Nanotextured Surfaces

ABSTRACT

The invention describes novel compositions that include a cross linking compound, a polymer and a 1 nm to about a 25 micron sized particle optionally with an oxide layer. In particular, the particle is a silica and one which has been pretreated with a silane.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims benefit under 35 U.S.C. §119(e) to U.S. Ser.Nos. 60/699,200, entitled “Nanotextured Surfaces”, filed Jul. 14, 2005(attorney docket number 186805/US) and 60/807,143, entitled“Nanotextured Surfaces”, filed Jul. 12, 2006 (attorney docket number186805/US/2), the contents of which are incorporated herein by referencein their entirety.

FIELD OF THE INVENTION

The invention relates generally to super hydrophobic or ultrahydrophobic coatings that include a cross linker with photoactivatablegroups, a polymer and a 1 nm to about a 25 micron sized particle,optionally with an oxide layer, such as a porous or non-porous silica.The compositions are useful as surface coating agents alone or incombination with other target molecules such as polymers, biomoleculesand the like.

BACKGROUND OF THE INVENTION

There exist many ways to coat, adhere, adsorb, modify, etc. a surfacewith a material, such that the material changes the characteristics ofthe surface. For example, suitable coatings can be prepared that whenapplied to a given surface render the surface hydrophobic. In otherinstances, the coating may provide enhanced ability to bind with atarget molecule, such as a protein.

In particular, there are known cross linking materials that include alatent reactive group, such as a photoactivatable group. The crosslinking material has, in general, at least two photoactivatable groups,such that one group can be activated and attached to the surface of thesubstrate. The remaining latent group, can then later be, orsimultaneously with the surface attachment, activated to react with atarget molecule such as a polymer or a biomolecule.

Unfortunately, the cross linking materials themselves are generally nothydrophobic and thus lessen the hydrophobic nature of the treatedsurface.

Therefore, a need exists for coating compositions that includephotoactivatable crosslinking groups that do not detract from thedesired hydrophobic nature of the treated surface.

BRIEF SUMMARY OF THE INVENTION

The present invention surprisingly provides unique hydrophobic or ultrahydrophobic compositions that include a crosslinker withphotoactivatable (photoreactive) groups, a polymer and a 1 nm to about a25 micron sized particle, optionally having an oxide layer, such as aporous or non-porous particles including, aluminum oxides (alumina),titanium oxide, zirconium oxide, gold (treated with thiols), silver(thiol or silane treated), nickel, iron oxide, and alloys (all treatedwith silane), polystyrene particles, (meth)acrylates particles, PTFEparticles, silica particles, polyolefin particles, polycarbonateparticles, polysiloxane particles, silicone particles, polyesterparticles, polyamide particles, polyurethane particles, ethylenicallyunsaturated polymer particles, polyanhydride particles and biodegradableparticles such as polycaprolactone (PCL) and polylactideglycolide(PLGA), and nanofibers, nanotubes, or nanowires. Generally inorganicparticles, porous or non-porous, are pretreated with a silane to promotehydrophobicity.

One unique cross linking molecular family includes compounds having theformula:

L-((D-T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m).

L is a linking group. D is O, S, SO, SO₂, NR⁵ or CR⁶R⁷. T is(—CH₂—)_(x), (—CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond. R^(l) is a hydrogen atom, analkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group. X is O,S, or NR⁸R⁹. P is a hydrogen atom or a protecting group, with theprovisio that P is absent when X is NR⁸R⁹. R² is a hydrogen atom, analkyl, alkyloxyalkyl, aryl, aryloxylalkyl or aryloxyaryl group. G is O,S, SO, SO₂, NR¹⁰, (CH₂)_(t)—O— or C═O. R³ and R⁴ are each independentlyan alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, oroptionally, R³ and R⁴ can be tethered together via (—CH₂—)_(q),(—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s), (—CH₂—)_(r)S(O)₂(—CH₂—)_(s), or(—CH₂—)_(r)NR(—CH₂—)_(s). R⁵ and R¹⁰ are each independently a hydrogenatom or an alkyl, aryl, or arylalkyl group. R⁶ and R⁷ are eachindependently a hydrogen atom, an alkyl, aryl, arylalkyl, heteroaryl orheteroarylalkyl group. R⁸ and R⁹ are each independently a hydrogen atom,an alkyl, aryl, or arylalkyl group, R is a hydrogen atom, an alkyl groupor an aryl group, q is an integer from 1 to about 7, r is an integerfrom 0 to about 3, s is an integer from 0 to about 3, m is an integerfrom 2 to about 10, t is an integer from 1 to about 10 and x is aninteger from 1 to about 500.

In one aspect, L is a branched or unbranched alkyl chain having betweenabout 2 and about 10 carbon atoms.

In another aspect, D is an oxygen atom (O).

In still another aspect, T is (—CH₂—)_(x) or (—CH₂CH₂—O—)_(x) and x is 1or 2.

In still yet another aspect, R¹ is a hydrogen atom.

In yet another aspect, X is an oxygen atom, O, and P is a hydrogen atom.

In another aspect, R² is a hydrogen atom.

In still another aspect, G is an oxygen atom, O.

In still yet another aspect, R³ and R⁴ are each individually arylgroups, which can be further substituted, and m is 3.

In one particular aspect, L is

D is O, T is (—CH₂—)_(x), R¹ is a hydrogen atom, X is O, P is a hydrogenatom, R² is a hydrogen atom, G is O, R³ and R⁴ are phenyl groups, m is 3and x is 1.

In yet another particular aspect, L is (—CH₂—)_(y), D is O, T is(—CH₂—)_(x), R¹ is a hydrogen atom, X is O, P is a hydrogen atom, R² isa hydrogen atom, G is O, R³ and R⁴ are phenyl groups, m is 2, x is 1 andy is an integer from 2 to about 6, and in particular, y is 2, 4 or 6.

A second unique cross linking molecular family includes compounds havingthe formula:

L-((T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m).

L is a linking group. T is (—CH₂—)_(x), (—CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond. R¹ is aatom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group.X is O, S, or NR⁸R⁹. P is a hydrogen atom or a protecting group, withthe provisio that P is absent when X is NR⁸R⁹. R² is a hydrogen atom, analkyl, alkyloxyalkyl, aryl, aryloxylalkyl or aryloxyaryl group. G is O,S, SO, SO₂, NR¹⁰, (CH₂)_(t)—O— or C═O. R³ and R⁴ are each independentlyan alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, oroptionally, R³ and R⁴ can be tethered together via (—CH₂—)_(q),(—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s), (—CH₂—)_(r)S(O)₂(—CH₂—)_(s), or(—CH₂—)_(r)NR(—CH₂—)_(s). R¹⁰ is a hydrogen atom or an alkyl, aryl, orarylalkyl group. R⁸ and R⁹ are each independently a hydrogen atom, analkyl, aryl, or arylalkyl group. R is a hydrogen atom, an alkyl group oran aryl group, q is an integer from 1 to about 7, r is an integer from 0to about 3, s is an integer from 0 to about 3, m is an integer from 2 toabout 10, t is an integer from 1 to about 10 and x is an integer from 1to about 500.

In one aspect, L has a formula according to structure (I):

A and J are each independently a hydrogen atom, an alkyl group, an arylgroup, or together with B form a cyclic ring, provided when A and J areeach independently a hydrogen atom, an alkyl group, or an aryl groupthen B is not present, B is NR¹¹, O, or (—CH₂—)_(z), provided when A, Band J form a ring, then A and J are (—CH₂—)_(z) or C═O, R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond with T,each z independently is an integer from 0 to 3 and provided when eitherA or J is C═O, then B is NR¹¹, O, or (—CH₂—)_(z) and z must be at least1.

In another aspect T is —CH₂—.

In still another aspect, R¹ is a hydrogen atom.

In still yet another aspect, X is O and P is a hydrogen atom.

In still another aspect, R² is a hydrogen atom.

In yet another aspect, G is O.

In another aspect, R³ and R⁴ are each individually aryl groups.

In still yet another aspect, m is 3, and in particular, A and J are bothC═O and B is N or A and J are both hydrogen atoms.

A third unique cross linking molecular family includes compounds havingthe formula:

L-((TGQR³C(═O)R⁴))_(m).

L is a linking group. T is (—CH₂—)_(x), (—CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond. G is O, S,SO, SO₂, NR¹⁰, (CH₂)_(t)—O— or C═O. Q is (—CH₂—)_(p), (—CH₂CH₂—O—)_(p),—(CH₂CH₂CH₂—O—)_(p) or (—CH₂CH₂CH₂CH₂—O—)_(p). R³ and R⁴ are eachindependently an alkyl, aryl, arylalkyl, heteroaryl, or anheteroarylalkyl group, or optionally, R³ and R⁴ can be tethered together(—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s), (—CH₂—)_(r)S(O)₂(—CH₂—)_(s), or(—CH₂—)_(r)NR(—CH₂—)_(s). R¹⁰ is a hydrogen atom or an alkyl, aryl,alkylaryl or arylalkyl group. R is a hydrogen atom, an alkyl group or anaryl group, q is an integer from 1 to about 7, r is an integer from 0 toabout 3, s is an integer from 0 to about 3, m is an integer from 2 toabout 10, p is an integer from 1 to about 10, t is an integer from 1 toabout 10 and x is an integer from 1 to about 500.

In one aspect, L has a formula according to structure (I):

A and J are each independently a hydrogen atom, an alkyl group, an arylgroup, or together with B form a cyclic ring, provided when A and J areeach independently a hydrogen atom, an alkyl group, or an aryl groupthen B is not present, B is NR¹¹, O, or (—CH₂—)_(z), provided when A, Band J form a ring, then A and J are (—CH₂—)_(z) or C═O, R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond with T,each z independently is an integer from 0 to 3 and provided when eitherA or J is C═O, then B is NR¹¹, O, or (—CH₂—)_(z) and z must be at least1.

In one aspect, T is —CH₂—.

In another aspect, G is an oxygen atom, O.

In still another aspect, R³ and R⁴ are each individually aryl groups,which can be substituted, and m is 2.

In still yet another aspect, A and J are both C═O and B is NR¹¹.

In another aspect, A and J are both hydrogen atoms.

In yet another aspect, L has a formula according to structure (II):

R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are each independently a hydrogen atom, analkyl or aryl group or denotes a bond with T, provided at least two ofR¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are bonded with T and each K, independentlyis CH or N.

A fourth unique cross linking molecular family includes compounds havingthe formula:

L-((GTZR³C(═O)R⁴))_(m)

L is a linking group. T is (—CH₂—)_(x), (—CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond. G is O, S,SO, SO₂, NR¹⁰, (CH₂)_(t)—O— or C═O. Z can be a C═O, COO or CONH when Tis (—CH₂—)_(x). R³ and R⁴ are each independently an alkyl, aryl,arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R³and R⁴ can be tethered together via (—CH₂—)_(q),(—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s), (—CH₂—)_(r)S(O)₂(—CH₂—)_(s), or(—CH₂—)_(r)NR(—CH₂—)_(s). R¹⁰ is a hydrogen atom or an alkyl, aryl,alkylaryl or arylalkyl group. R is a hydrogen atom, an alkyl group or anaryl group, q is an integer from 1 to about 7, r is an integer from 0 toabout 3, s is an integer from 0 to about 3, m is an integer from 2 toabout 10, p is an integer from 1 to about 10, t is an integer from 1 toabout 10 and x is an integer from 1 to about 500.

In one aspect, L has a formula according to structure (I):

A and J are each independently a hydrogen atom, an alkyl group, an arylgroup, or together with B form a cyclic ring, provided when A and J areeach independently a hydrogen atom, an alkyl group, or an aryl groupthen B is not present, B is NR¹¹, O, or (—CH₂—)_(z), provided when A, Band J form a ring, then A and J are (—CH₂—)_(z) or C═O, R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond with T,each z independently is an integer from 0 to 3 and provided when eitherA or J is C═O, then B is NR¹¹, O, or (—CH₂—)_(z) and z must be at least1.

In one aspect, T is —CH₂—.

In another aspect, G is an oxygen atom, O.

In still another aspect, R³ and R⁴ are each individually aryl groups,which can be substituted, and m is 2.

In still yet another aspect, A and J are both C═O and B is NR¹¹.

In another aspect, A and J are both hydrogen atoms.

In yet another aspect, L has a formula according to structure (II):

R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are each independently a hydrogen atom, analkyl or aryl group or denotes a bond with T, provided at least two ofR¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are bonded with T and each K, independentlyis CH or N.

In still yet another aspect, compounds of the present invention providethat R³ and R⁴ are both phenyl groups and are tethered together via aCO, a S or a CH₂.

In yet another aspect, compounds of the present invention provide whenR³ and R⁴ are both phenyl group, the phenyl groups can be substitutedwith at least one CH₃OCH₂CH₂O—.

The compositions of the invention include the crosslinkers describedthroughout the specification in combination with a polymer, inparticular a hydrophobic polymer, and a particle having a particle sizebetween about 1 nm to about a 25 microns, such as a porous or non-poroussilica. In one embodiment, the particle has been treated with a silane.

The compositions of the invention have broad applications. Thecompositions can be used in surface modifications. The combination ofthe crosslinker, polymer, and particle, optionally treated with silane,having a size between about 1 nm to about a 25 microns, such as silica,provide hydrophobic coatings. This physical attribute provides that thecompositions can be used where hydrophobic agents are favored.

The inclusion of photoreactive moieties within the compositions providesthat the composition can be used with a wide range of support surfaces.The compositions can be used alone or in combination with othermaterials to provide a desired surface characteristic. The compositions,alone or in combination with another material, provides the treatedsurface having a hydrophobic surface.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description. As will be apparent, the inventionis capable of modifications in various obvious aspects, all withoutdeparting from the spirit and scope of the present invention.Accordingly, the detailed descriptions are to be regarded asillustrative in nature and not restrictive.

DETAILED DESCRIPTION

The present invention surprisingly provides unique cross linkingmolecule families that include photoactivatable groups, that incombination with a polymer and a 1 nm to about a 25 micron sizedparticle, such as silica, provide hydrophobic (e.g., super hydrophobicor ultra hydrophobic) compositions that can be used to treat surfaces.

The compositions of the invention are useful as coating agents. Asdescribed throughout the specification, the compositions include aunique crosslinker, a polymer and a particle having a particle sizebetween about 1 nm to about a 25 microns. In one embodiment, theparticle has an oxide coating. In another aspect, the particle ispretreated with a silane. In still another aspect, the particle, withthe oxide layer has been pretreated with a silane. The intent being thatthe particle exhibits some degree of hydrophobicity.

The particles include those particles having a particle size of betweenabout 1 nm and about 25 micron sized particles that can be porous ornon-porous particles derived from aluminum oxides (alumina), titaniumoxide, zirconium oxide, gold (treated with thiols), silver (thiol orsilane treated), nickel, iron oxide, and alloys (all treated withsilane), polystyrene particles,(meth)acrylates particles, PTFEparticles, silica particles, polyolefin particles, polycarbonateparticles, polysiloxane particles, silicone particles, polyesterparticles, polyamide particles, polyurethane particles, ethylenicallyunsaturated polymer particles, polyanhydride particles and biodegradableparticles such as polycaprolactone (PCL) and polylactideglycolide(PLGA), and nanofibers, nanotubes, or nanowires and combinationsthereof. Appropriate treatments of the metals, such as gold, silver, andother nobel metals and alloys are generally include use of alkylthiols,more particularly fluoroalkylthiols.

Super hydrophobicity, and ultra hydrophobicity are defined as surfaceswhich have a water contact angle above 150° and 120°-150° respectively.In nature, lotus leaves are considered super hydrophobic. Water dropsroll off the leaves collecting dirt along the way to give a“self-cleaning” surface. This behavior is believed to be a result ofnanotextured surfaces, as well as a wax layer present on the leaf.However, super hydrophobic surfaces cannot be derived from simplycoating hydrophobic or oleophobic substances on surfaces, but alsorequire nanotexture, small protrusions on the surface giving atopography on the order of 1-1000 nm. When nanotexture is added to ahydrophobic surface, water contact angles rise from 100-120° to over150°. Not to be limited by theory, it is believed that the nanotextureproduces this effect by trapping air in the spaces between structuralfeatures. Water droplets interact with both the very small hydrophobictips of the particles and the larger valleys between particles whereonly air remains. Air is also highly hydrophobic. The water contacts theparticle tips and does not penetrate into the air pockets. As a resultthe water cannot remain still on the surface and “dances” away.

The present invention provides unique compositions and methods forpreparing photocrosslinked super hydrophobic or ultra hydrophobicsurfaces. Such surfaces may be useful for coatings for a variety ofapplications including automotive, RF coatings for satellite dishes,fabrics, filters, transportation, building materials, and others. Thereare few low cost methods of manufacturing super or ultra hydrophobicsurfaces and these current methods generally lack durability.Introducing photoreactive crosslinkers into a polymer-particle matrixand photolyzing the crosslinker, crosslinks the matrix and greatlyimproves durability and use time of the coatings.

The coatings of the invention can be applied to a large variety ofsubstrates including but not limited to plastics (polyethylene, PVC,polystyrene, polyurethane, etc), glass, wood, paper, ceramics andmetals. The polymer is optimally hydrophobic (WCA >70°) and may containreactive groups such as double bonds, but is not required to. Thephotocrosslinker may be hydrophobic, amphiphilic, or hydrophilic as itis added in smaller quantities. The nanoparticles should also behydrophobic. The polymer matrix entraps the nanoparticles on the surfaceto give the needed nanotexture. It also provides the surfacehydrophobicity.

Photopolymerization can be defined as a phenomenon whereby low molecularweight substances are joined together to create a new larger structureby way of the action of light. When light is absorbed, electronspopulate excited states in molecules. These excited states are generallyquite short-lived and terminate by one of three pathways. The excitedstate can emit a photon from either a singlet state (fluorescence) or atriplet state (phosphorescence), lose its energy via vibrations in theform on heat, or react chemically. Because the absorption of a photonhighly excites a molecule, there is a much wider variety of reactionspossible than standard thermochemical means. Photocrosslinking usesthese reactions to link small molecules to other small molecules, largemolecules to small molecules, and large molecules to each other(photocoupling of polymers), as well as large and small molecules tosubstrates or particles (photobonding to surfaces). Duringphotocrosslinking each increase in molecular weight is initiated by itsown photochemical reaction and the coupling of radicals can result inthe formation of crosslinks, especially in the solid state. Thecrosslinking is generally between pre-existing polymer chains andincludes polycondensation, which is also referred to as step growthpolymerization. Photocrosslinking can usually be classified into twotypes.

The first type is where crosslinks are formed by the direct reaction ofan excited molecule. Representative reactions would be a photo 2+2cycloaddition (or 4+4) and cis-trans isomerization of double bonds.Examples of this type are demonstrated by the cyclodimerization ofcinnamic acid and derivatives, chalcones and stilbenes, anthracenes,maleimides and strained cycloalkenes. In another large class ofreactions, the triplet, T₁ excited state of carbonyl groups in ketonescan result in either fragmentation (Norrish Type I reaction) or hydrogenabstraction (Norrish type II reaction). Both of these photoreactionscreate two radicals which can then subsequently react with surroundingmolecules. For example, aromatic ketones, such as benzophenone, readilyundergo hydrogen abstraction reactions with any preformed polymerpossessing C—H bonds. A possible mechanism is shown in the Scheme whichfollows.

(C₆H₅)₂C═O)(T₁)+Rp-H→(C₆H₅)₂C.—OH)+Rp.

Rp.+(C₆H₅)₂C.—OH)→(C₆H₅)₂C-(Rp)-OH)

Scheme. Possible photolysis mechanism with benzophenone as an example ofa non cross linking photoreactive moiety. It should be understood thatincorporation of two or more photoreactive moieties, such as abenzophenone, would provide a multifunctional cross linkingphotoreactive group.

The second usual type of photocrosslinking is where crosslinks occurthrough the action of a photogenerated reactive species. Examples of thesecond type include the use of nitrenes that are formed from organicazides, carbenes.

Whether through direct excited state reaction or reactive intermediates,photolysis of photoreactive cross linking groups can begin a process ofbond formation throughout a mixture. In most cases this will be a solidmixture of polymers, particles, and photoreactive cross linking groupsdesigned to give a nanotextured surface. The act of cross linking willserve to increase the durability of this surface. Bonds will be formedbetween polymer and photoreactive cross linking group, and betweenpolymer, photoreactive cross linking group and the surface and/orparticles. Bond formation may take place by many means within thevarious systems. In many cases radicals are formed through photolysis.Radicals can form new bonds through radical-radical recombination,addition to unsaturated bonds, hydrogen abstraction and subsequentrecombination or addition, further fragmentation, oxygen addition, ordisproportionation, as well as possible electron transfer reactions.Similarly, photoreactive cross linking group and polymer can be bondedto the surface of the substrate or the particles. All of these newlyformed covalent bonds increase the durability and stability of thematrix. In cases which generate carbenes and nitrenes, bonds would beformed typically by insertion, hydrogen abstraction to form radicals,rearrangements, etc. The excited states of some dienes and otherunsaturated compounds may directly react with relevant groups on apolymer chain, as when cinnamic acid forms a 2+2 photoadduct withpolybutadiene or other polymer (or surface) containing double bonds. Theinvention is not limited to these mechanisms, and in fact, manymechanisms may be at work within one polymer-particle-photoreactivecross linking group matrix.

In one embodiment the crosslinker has the formula:

L-((D-T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m).

L is a linking group. D is O, S, SO, SO₂, NR⁵ or CR⁶R⁷. T is(—CH₂—)_(x), (—CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond. R¹ is a hydrogen atom, an alkyl,alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group. X is O, S, orNR⁸R⁹. P is a hydrogen atom or a protecting group, with the provisiothat P is absent when X is NR⁸R⁹. R² is a hydrogen atom, an alkyl,alkyloxyalkyl, aryl, aryloxylalkyl or aryloxyaryl group. G is O, S, SO,SO₂, NR¹⁰, (CH₂)_(t)—O— or C═O. R³ and R⁴ are each independently analkyl, aryl, arylalkyl, heteroaryl, or a heteroarylalkyl group, oroptionally, R³ and R⁴ can be tethered together via (—CH₂—)_(q),(—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s), (—CH₂—)_(r)S(O)₂(—CH₂—)_(s), or(—CH₂—)_(r)NR(—CH₂—)_(s). R⁵ and R¹⁰ are each independently a hydrogenatom or an alkyl, aryl, or arylalkyl group. R⁶ and R⁷ are eachindependently a hydrogen atom, an alkyl, aryl, arylalkyl, heteroaryl orheteroarylalkyl group. R⁸ and R⁹ are each independently a hydrogen atom,an alkyl, aryl, or arylalkyl group, R is a hydrogen atom, an alkyl groupor an aryl group, q is an integer from 1 to about 7, r is an integerfrom 0 to about 3, s is an integer from 0 to about 3, m is an integerfrom 2 to about 10, t is an integer from 1 to about 10 and x is aninteger from 1 to about 500.

In one aspect, L is a branched or unbranched alkyl chain having betweenabout 2 and about 10 carbon atoms.

In another aspect, D is an oxygen atom (O).

In still another aspect, T is (—CH₂—)_(x) or (—CH₂CH₂—O—)_(x) and x is 1or 2.

In still yet another aspect, R¹ is a hydrogen atom.

In yet another aspect, X is an oxygen atom, O, and P is a hydrogen atom.

In another aspect, R² is a hydrogen atom.

In still another aspect, G is an oxygen atom, O.

In still yet another aspect, R³ and R⁴ are each individually arylgroups, which can be further substituted, and m is 3.

In one particular aspect, L is

D is O, T is (—CH₂—)_(x), R¹ is a hydrogen atom, X is O, P is a hydrogenatom, R² is a hydrogen atom, G is O, R³ and R⁴ are phenyl groups, m is 3and x is 1.

In yet another particular aspect, L is (—CH₂—)_(y), D is O, T is(—CH₂—)_(x), R¹ is a hydrogen atom, X is O, P is a hydrogen atom, R² isa hydrogen atom, G is O, R³ and R⁴ are phenyl groups, m is 2, x is 1 andy is an integer from 2 to about 6, and in particular, y is 2, 4 or 6.

In certain embodiments, x is an integer from about 1 to about 500, moreparticularly from about 1 to about 400, from about 1 to about 250, fromabout 1 to about 200, from about 1 to about 150, from about 1 to about100, from about 1 to about 50, from about 1 to about 25 or from about 1to about 10.

In another embodiment, the crosslinker has the formula:

L-((T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m).

wherein L, T, R¹, X, P, R², G, R³, R⁴, R⁸, R⁹, R¹⁰, R, q, r, s, m and xare as defined above.

In one aspect, L has a formula according to structure (I):

A and J are each independently a hydrogen atom, an alkyl group, an arylgroup, or together with B form a cyclic ring, provided when A and J areeach independently a hydrogen atom, an alkyl group, or an aryl groupthen B is not present, B is NR¹¹, O, or (—CH₂—)_(z), provided when A, Band J form a ring, then A and J are (—CH₂—)_(z) or C═O, R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond with T,each z independently is an integer from 0 to 3 and provided when eitherA or J is C═O, then B is NR¹¹, O, or (—CH₂—)_(z) and z must be at least1.

In another aspect T is —CH₂—.

In another embodiment, the family has the formula:

L-((GTZR³C(═O)R⁴))_(m)

wherein L, T, G, R³, R⁴, R¹⁰, R, q, r, s, m and x are as defined above.Z can be a C═O, COO or CONH when T is (—CH₂—)_(x).

In one aspect, L has a formula according to structure (I):

wherein A, B, J, R¹¹, and z are as defined above.

In another aspect, L has a formula according to structure (II):

R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are each independently a hydrogen atom, analkyl or aryl group or denotes a bond with T, provided at least two ofR¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are bonded with T and each K, independentlyis CH or N.

In another embodiment, the family has the formula:

L-((TGQR³C(═O)R⁴))_(m)

wherein L, G, R³, R⁴, R¹⁰, R, q, r, s, m and x are as defined above. Tis (—CH₂—)_(x), (—CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond. Q is (—CH₂—)_(p),(—CH₂CH₂—O—)_(p), (—CH₂CH₂CH₂—O—)_(p) or (—CH₂CH₂CH₂CH₂—O—)_(p) and p isan integer from 1 to about 10.

In one aspect, L has a formula according to structure (I):

wherein A, B, J, R¹¹, and z are as defined above.

In another aspect, L has a formula according to structure (II):

R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are each independently a hydrogen atom, analkyl or aryl group or denotes a bond with T, provided at least two ofR¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are bonded with T and each K, independentlyis CH or N.

In still yet another aspect, compounds of the present invention providethat R³ and R⁴ are both phenyl groups and are tethered together via aCO, a S or a CH₂.

In yet another aspect, compounds of the present invention provide whenR³ and R⁴ are phenyl groups, the phenyl groups can each independently besubstituted with at least one alkyloxyalkyl group, such asCH₃O—(CH₂CH₂O—)_(n)—, or CH₃O(—CH₂CH₂CH₂O—)_(n)— a hydroxylated alkoxygroup, such as HO—CH₂CH₂O—, HO(—CH₂CH₂O—)_(n)— or HO(—CH₂CH₂CH₂O—)_(n)—,etc. wherein n is an integer from 1 to about 10.

In another embodiment the family has the formula:

L-((-CH₂—)_(xx)C(R¹)(GR³C(═O)R⁴)₂)_(m)

wherein L, each R, R¹, each G, each R³, each R⁴, each R¹⁰, each q, eachr, each s, each t and m are as defined above and xx is an integer from 1to about 10.

In one aspect, L has a formula according to structure (I):

wherein A, B, J, R¹¹, and z are as defined above.

In another aspect, A and J are both hydrogen atoms.

In still another aspect, xx is 1.

In yet another aspect, R¹ is H.

In still yet another aspect, G is (—CH₂O—)_(t)O— and t is 1.

In another aspect, R³ and R⁴ are each individually aryl groups.

In still yet another embodiment, xx is 1, R¹ is H, each G is(—CH₂—)_(t)O—, t is 1 and each of R³ and R⁴ are each individually arylgroups.

In another embodiment of the invention, the family has the formula:

L-((-C(R¹)(XP)CHR²GR³C(═O)R⁴)_(m)

where L, R, R¹, R², R³, R⁴, R⁸, R⁹, R¹⁰, X, P, G, q, r, s, t, and m areas defined above.

In one aspect, L is

and R²⁰ and R²¹ are each individually a hydrogen atom, an alkyl group oran aryl group.

In another aspect, R¹ is H.

In still another aspect, X is O.

In yet another aspect, P is H.

In still yet another aspect, R² is H.

In another aspect, G is (—CH₂-)tO— and t is 1.

In still another aspect, R³ and R⁴ are each individually aryl groups.

In yet another aspect, R¹ is H, X is O, P is H, R² is H, G is(—CH₂—)_(t)O—, t is 1, R³ and R⁴ are each individually aryl groups andR²⁰ and R²¹ are both methyl groups.

In yet another embodiment, the present invention provides a family ofcompounds having the formula:

L-((GR³C(═O)R⁴))_(m)

where L, G, R, R³, R⁴, R¹⁰, q, r, s, m and t are as defined above.

In one aspect, L is

In another aspect, G is C═O.

In still another aspect, R³ and R⁴ are each individually aryl groups.

In yet another aspect, G is C═O and R³ and R⁴ are each individually arylgroups.

In still yet another embodiment, the present invention provides a familyof compounds having the formula:

L-((ZZ-D-T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m)

where L is as described above or CH.

T, R¹, X, P, R², G, R³, R⁴ and m are as described above.

ZZ is a linking group as described above for L, and in particular is anaryl or alkyl group. In particular ZZ is a phenyl group.

In one aspect, m is 3.

In another aspect, L is CH, ZZ is phenyl, D is O, T is CH₂, R¹ is H, Pis H, R² is H, G is O, R³ is phenyl, R⁴ is phenyl with a —OC₈H₁₇ (analkoxide) substituent and m is 3.

“Alkyl” by itself or as part of another substituent refers to asaturated or unsaturated branched, straight-chain or cyclic monovalenthydrocarbon radical having the stated number of carbon atoms (i.e.,C1-C6 means one to six carbon atoms) that is derived by the removal ofone hydrogen atom from a single carbon atom of a parent alkane, alkeneor alkyne. Typical alkyl groups include, but are not limited to, methyl;ethyls such as ethanyl, ethenyl, ethynyl; propyls such as propan-1-yl,propan-2-yl, cyclopropan-1-yl, prop-1-en-1-yl, prop-1-en-2-yl,prop-2-en-1-yl, cycloprop-1-en-1-yl; cycloprop-2-en-1-yl,prop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butyls such as butan-1-yl,butan-2-yl, 2-methyl-propan-1-yl, 2-methyl-propan-2-yl, cyclobutan-1-yl,but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl,but-2-en-2-yl, buta-1,3-dien-1-yl, buta-1,3-dien-2-yl,cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclobuta-1,3-dien-1-yl,but-1-yn-1-yl, but-1-yn-3-yl, but-3-yn-1-yl, etc.; and the like. Wherespecific levels of saturation are intended, the nomenclature “alkanyl,”“alkenyl” and/or “alkynyl” is used, as defined below. “Lower alkyl”refers to alkyl groups having from 1 to 6 carbon atoms.

“Alkanyl” by itself or as part of another substituent refers to asaturated branched, straight-chain or cyclic alkyl derived by theremoval of one hydrogen atom from a single carbon atom of a parentalkane. Typical alkanyl groups include, but are not limited to,methanyl; ethanyl; propanyls such as propan-1-yl, propan-2-yl(isopropyl), cyclopropan-1-yl, etc.; butanyls such as butan-1-yl,butan-2-yl (sec-butyl), 2-methyl-propan-1-yl (isobutyl),2-methyl-propan-2-yl (t-butyl), cyclobutan-1-yl, etc.; and the like.

“Alkenyl” by itself or as part of another substituent refers to anunsaturated branched, straight-chain or cyclic alkyl having at least onecarbon-carbon double bond derived by the removal of one hydrogen atomfrom a single carbon atom of a parent alkene. The group may be in eitherthe cis or trans conformation about the double bond(s). Typical alkenylgroups include, but are not limited to, ethenyl; propenyls such asprop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl, prop-2-en-2-yl,cycloprop-1-en-1-yl; cycloprop-2-en-1-yl; butenyls such asbut-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl,but-2-en-2-yl, buta-1,3-dien-1-yl, buta-1,3-dien-2-yl,cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclobuta-1,3-dien-1-yl, etc.;and the like.

“Alkyloxyalkyl” refers to a moiety having two alkyl groups tetheredtogether via an oxygen bond. Suitable alkyloxyalkyl groups includepolyoxyalkylenes, such as polyethyleneoxides, polypropyleneoxides, etc.that are terminated with an alkyl group, such as a methyl group. Ageneral formula for such compounds can be depicted as R′—(OR″)_(n) or(R′O)_(n)—R″ wherein n is an integer from 1 to about 10, and R′ and R″are alkyl or alkylene groups.

“Alkynyl” by itself or as part of another substituent refers to anunsaturated branched, straight-chain or cyclic alkyl having at least onecarbon-carbon triple bond derived by the removal of one hydrogen atomfrom a single carbon atom of a parent alkyne. Typical alkynyl groupsinclude, but are not limited to, ethynyl; propynyls such asprop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butynyls such as but-1-yn-1-yl,but-1-yn-3-yl, but-3-yn-1-yl, etc.; and the like.

“Alkyldiyl” by itself or as part of another substituent refers to asaturated or unsaturated, branched, straight-chain or cyclic divalenthydrocarbon group having the stated number of carbon atoms (i.e., C1-C6means from one to six carbon atoms) derived by the removal of onehydrogen atom from each of two different carbon atoms of a parentalkane, alkene or alkyne, or by the removal of two hydrogen atoms from asingle carbon atom of a parent alkane, alkene or alkyne. The twomonovalent radical centers or each valency of the divalent radicalcenter can form bonds with the same or different atoms. Typicalalkyldiyl groups include, but are not limited to, methandiyl; ethyldiylssuch as ethan-1,1-diyl, ethan-1,2-diyl, ethen-1,1-diyl, ethen-1,2-diyl;propyldiyls such as propan-1,1-diyl, propan-1,2-diyl, propan-2,2-diyl,propan-1,3-diyl, cyclopropan-1,1-diyl, cyclopropan-1,2-diyl,prop-1-en-1,1-diyl, prop-1-en-1,2-diyl, prop-2-en-1,2-diyl,prop-1-en-1,3-diyl, cycloprop-1-en-1,2-diyl, cycloprop-2-en-1,2-diyl,cycloprop-2-en-1,1-diyl, prop-1-yn-1,3-diyl, etc.; butyldiyls such as,butan-1,1-diyl, butan-1,2-diyl, butan-1,3-diyl, butan-1,4-diyl,butan-2,2-diyl, 2-methyl-propan-1,1-diyl, 2-methyl-propan-1,2-diyl,cyclobutan-1,1-diyl; cyclobutan-1,2-diyl, cyclobutan-1,3-diyl,but-1-en-1,1-diyl, but-1-en-1,2-diyl, but-1-en-1,3-diyl,but-1-en-1,4-diyl, 2-methyl-prop-1-en-1,1-diyl,2-methanylidene-propan-1,1-diyl, buta-1,3-dien-1,1-diyl,buta-1,3-dien-1,2-diyl, buta-1,3-dien-1,3-diyl, buta-1,3-dien-1,4-diyl,cyclobut-1-en-1,2-diyl, cyclobut-1-en-1,3-diyl, cyclobut-2-en-1,2-diyl,cyclobuta-1,3-dien-1,2-diyl, cyclobuta-1,3-dien-1,3-diyl,but-1-yn-1,3-diyl, but-1-yn-1,4-diyl, buta-1,3-diyn-1,4-diyl, etc.; andthe like. Where specific levels of saturation are intended, thenomenclature alkanyldiyl, alkenyldiyl and/or alkynyldiyl is used. Whereit is specifically intended that the two valencies be on the same carbonatom, the nomenclature “alkylidene” is used. A “lower alkyldiyl” is analkyldiyl group having from 1 to 6 carbon atoms. In preferredembodiments the alkyldiyl groups are saturated acyclic alkanyldiylgroups in which the radical centers are at the terminal carbons, e.g.,methandiyl (methano); ethan-1,2-diyl (ethano); propan-1,3-diyl(propano); butan-1,4-diyl (butano); and the like (also referred to asalkylenes, defined infra).

“Alkylene” by itself or as part of another substituent refers to astraight-chain saturated or unsaturated alkyldiyl group having twoterminal monovalent radical centers derived by the removal of onehydrogen atom from each of the two terminal carbon atoms ofstraight-chain parent alkane, alkene or alkyne. The locant of a doublebond or triple bond, if present, in a particular alkylene is indicatedin square brackets. Typical alkylene groups include, but are not limitedto, methylene (methano); ethylenes such as ethano, etheno, ethyno;propylenes such as propano, prop[1]eno, propa[1,2]dieno, prop[1]yno,etc.; butylenes such as butano, but[1]eno, but[2]eno, buta[1,3]dieno,but[1]yno, but[2]yno, buta[1,3]diyno, etc.; and the like. Where specificlevels of saturation are intended, the nomenclature alkano, alkenoand/or alkyno is used. In preferred embodiments, the alkylene group is(C1-C6) or (C1-C3) alkylene. Also preferred are straight-chain saturatedalkano groups, e.g., methano, ethano, propano, butano, and the like.

“Aryl” by itself or as part of another substituent refers to amonovalent aromatic hydrocarbon group having the stated number of carbonatoms (i.e., C5-C15 means from 5 to 15 carbon atoms) derived by theremoval of one hydrogen atom from a single carbon atom of a parentaromatic ring system. Typical aryl groups include, but are not limitedto, groups derived from aceanthrylene, acenaphthylene,acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene,fluoranthene, fluorene, hexacene, hexaphene, hexalene, as-indacene,s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene,ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene,phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene,rubicene, triphenylene, trinaphthalene, and the like, as well as thevarious hydro isomers thereof. In preferred embodiments, the aryl groupis (C5-C15) aryl, with (C5-C10) being even more preferred. Particularlypreferred aryls are phenyl and naphthyl.

“Arylalkyl” by itself or as part of another substituent refers to anacyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced withan aryl group. Typical arylalkyl groups include, but are not limited to,benzyl, 2-phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl,2-naphthylethan-1-yl, 2-naphthylethen-1-yl, naphthobenzyl,2-naphthophenylethan-1-yl and the like. Where specific alkyl moietiesare intended, the nomenclature arylalkanyl, arylalkenyl and/orarylalkynyl is used. Preferably, an arylalkyl group is (C₇-C₃₀)arylalkyl, e.g., the alkanyl, alkenyl or alkynyl moiety of the arylalkylgroup is (C₁-C₁₀) and the aryl moiety is (C₆-C₂₀), more preferably, anarylalkyl group is (C₇-C₂₀) arylalkyl, e.g., the alkanyl, alkenyl oralkynyl moiety of the arylalkyl group is (C₁-C₈) and the aryl moiety is(C₆-C₁₂).

“Aryloxyalkyl” refers to a moiety having an aryl group and an alkylgroup tethered together via an oxygen bond. Suitable aryloxyalkyl groupsinclude phenyloxyalkylenes, such as methoxyphenyl, ethoxyphenyl, etc.

“Cycloalkyl” by itself or as part of another substituent refers to acyclic version of an “alkyl” group. Typical cycloalkyl groups include,but are not limited to, cyclopropyl; cyclobutyls such as cyclobutanyland cyclobutenyl; cyclopentyls such as cyclopentanyl and cycloalkenyl;cyclohexyls such as cyclohexanyl and cyclohexenyl; and the like.

“Cycloheteroalkyl” by itself or as part of another substituent refers toa saturated or unsaturated cyclic alkyl radical in which one or morecarbon atoms (and any associated hydrogen atoms) are independentlyreplaced with the same or different heteroatom. Typical heteroatoms toreplace the carbon atom(s) include, but are not limited to, N, P, O, S,Si, etc. Where a specific level of saturation is intended, thenomenclature “cycloheteroalkanyl” or “cycloheteroalkenyl” is used.Typical cycloheteroalkyl groups include, but are not limited to, groupsderived from epoxides, imidazolidine, morpholine, piperazine,piperidine, pyrazolidine, pyrrolidine, quinuclidine, and the like.

“Halogen” or “Halo” by themselves or as part of another substituent,unless otherwise stated, refer to fluoro, chloro, bromo and iodo.

“Haloalkyl” by itself or as part of another substituent refers to analkyl group in which one or more of the hydrogen atoms are replaced witha halogen. Thus, the term “haloalkyl” is meant to includemonohaloalkyls, dihaloalkyls, trihaloalkyls, etc. up to perhaloalkyls.For example, the expression “(C1-C2) haloalkyl” includes fluoromethyl,difluoromethyl, trifluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl,1,2-difluoroethyl, 1,1,1-trifluoroethyl, perfluoroethyl, etc.

“Heteroalkyl, Heteroalkanyl, Heteroalkenyl, Heteroalkynyl” by itself oras part of another substituent refer to alkyl, alkanyl, alkenyl andalkynyl radical, respectively, in which one or more of the carbon atoms(and any associated hydrogen atoms) are each independently replaced withthe same or different heteroatomic groups. Typical heteroatomic groupsinclude, but are not limited to, —O—, —S—, —O—O—, —S—S—, —O—S—, —NR′—,═N—N═, —N═N—, —N═N—NR′—, —PH—, —P(O)₂—, —O—P(O)₂—, —S(O)—, —S(O)₂—,—SnH₂— and the like, where R′ is hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, aryl or substituted aryl.

“Heteroaryl” by itself or as part of another substituent, refers to amonovalent heteroaromatic radical derived by the removal of one hydrogenatom from a single atom of a parent heteroaromatic ring system. Typicalheteroaryl groups include, but are not limited to, groups derived fromacridine, arsindole, carbazole, β-carboline, benzoxazine, benzimidazole,chromane, chromene, cinnoline, furan, imidazole, indazole, indole,indoline, indolizine, isobenzofuran, isochromene, isoindole,isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine,oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline,phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole,pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline,quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole,thiophene, triazole, xanthene, and the like. Preferably, the heteroarylgroup is from 5-20 membered heteroaryl, more preferably from 5-10membered heteroaryl. Preferred heteroaryl groups are those derived fromthiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine,quinoline, imidazole, oxazole and pyrazine.

“Heteroarylalkyl” by itself or as part of another substituent refers toan acyclic alkyl group in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with aheteroaryl group. Where specific alkyl moieties are intended, thenomenclature heteroarylalkanyl, heteroarylakenyl and/orheteroarylalkynyl is used. In preferred embodiments, the heteroarylalkylgroup is a 6-21 membered heteroarylalkyl, e.g., the alkanyl, alkenyl oralkynyl moiety of the heteroarylalkyl is (C1-C6) alkyl and theheteroaryl moiety is a 5-15-membered heteroaryl. In particularlypreferred embodiments, the heteroarylalkyl is a 6-13 memberedheteroarylalkyl, e.g., the alkanyl, alkenyl or alkynyl moiety is (C1-C3)alkyl and the heteroaryl moiety is a 5-10 membered heteroaryl.

“Hydroxyalkyl” by itself or as part of another substituent refers to analkyl group in which one or more of the hydrogen atoms are replaced witha hydroxyl substituent. Thus, the term “hydroxyalkyl” is meant toinclude monohydroxyalkyls, dihydroxyalkyls, trihydroxyalkyls, etc.

“Parent Aromatic Ring System” refers to an unsaturated cyclic orpolycyclic ring system having a conjugated π electron system.Specifically included within the definition of “parent aromatic ringsystem” are fused ring systems in which one or more of the rings arearomatic and one or more of the rings are saturated or unsaturated, suchas, for example, fluorene, indane, indene, phenalene,tetrahydronaphthalene, etc. Typical parent aromatic ring systemsinclude, but are not limited to, aceanthrylene, acenaphthylene,acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene,fluoranthene, fluorene, hexacene, hexaphene, hexalene, indacene,s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene,ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene,phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene,rubicene, tetrahydronaphthalene, triphenylene, trinaphthalene, and thelike, as well as the various hydro isomers thereof

“Parent Heteroaromatic Ring System” refers to a parent aromatic ringsystem in which one or more carbon atoms (and any associated hydrogenatoms) are independently replaced with the same or different heteroatom.Typical heteroatoms to replace the carbon atoms include, but are notlimited to, N, P, O, S, Si, etc. Specifically included within thedefinition of “parent heteroaromatic ring systems” are fused ringsystems in which one or more of the rings are aromatic and one or moreof the rings are saturated or unsaturated, such as, for example,arsindole, benzodioxan, benzofuran, chromane, chromene, indole,indoline, xanthene, etc. Typical parent heteroaromatic ring systemsinclude, but are not limited to, arsindole, carbazole, β-carboline,chromane, chromene, cinnoline, furan, imidazole, indazole, indole,indoline, indolizine, isobenzofuran, isochromene, isoindole,isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine,oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline,phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole,pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline,quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole,thiophene, triazole, xanthene, and the like.

“Leaving group” is a group that is displaced during a reaction by anucleophilic reagent. Suitable leaving groups include S(O)₂Me, —SMe orhalo (e.g., F, Cl, Br, I).

“Linking group” is a group that serves as an intermediate locus betweentwo or more end groups. The nature of the linking group can vary widely,and can include virtually any combination of atoms or groups useful forspacing one molecular moiety from another. For example, the linker maybe an acyclic hydrocarbon bridge (e.g, a saturated or unsaturatedalkyleno such as methano, ethano, etheno, propano, prop[1]eno, butano,but[1]eno, but[2]eno, buta[1,3]dieno, and the like), a monocyclic orpolycyclic hydrocarbon bridge (e.g., [1,2]benzeno, [2,3]naphthaleno, andthe like), a simple acyclic heteroatomic or heteroalkyldiyl bridge(e.g., —O—, —S—, —S—O—, —NH—, —PH—, —C(O)—, —C(O)NH—, —S(O)—, —S(O)₂—,—S(O)NH—, —S(O)₂NH—, —O—CH₂—, —CH₂—O—CH₂—, —O—CH═CH—CH₂—, and the like),a monocyclic or polycyclic heteroaryl bridge (e.g., [3,4]furano,pyridino, thiopheno, piperidino, piperazino, pyrazidino, pyrrolidino,and the like) or combinations of such bridges.

“Protecting group” is a group that is appended to, for example, ahydroxyl oxygen in place of a labile hydrogen atom. Suitable hydroxylprotecting group(s) include esters (acetate, ethylacetate), ethers(methyl, ethyl), ethoxylated derivatives (ethylene glycol, propyleneglycol) and the like that can be removed under either acidic or basicconditions so that the protecting group is removed and replaced with ahydrogen atom. Guidance for selecting appropriate protecting groups, aswell as synthetic strategies for their attachment and removal, may befound, for example, in Greene & Wuts, Protective Groups in OrganicSynthesis, 3d Edition, John Wiley & Sons, Inc., New York (1999) and thereferences cited therein (hereinafter “Greene & Wuts”).

The compositions of the invention that can be used as coating agentsinclude one or more moieties that render the molecule hydrophobic innature.

Photoreactive species are as described herein, and are sufficientlystable to be stored under conditions in which they retain suchproperties. See, e.g., U.S. Pat. No. 5,002,582, the disclosure of whichis incorporated herein by reference. Latent reactive groups can bechosen that are responsive to various portions of the electromagneticspectrum, with those responsive to ultraviolet, infrared and visibleportions of the spectrum (referred to herein as “photoreactive”).

Photoreactive groups respond to external stimuli and undergo activespecie generation with the formation of a covalent bond to an adjacentchemical structure, e.g., as provided by the same or a differentmolecule. Photoreactive groups are those groups of atoms in a moleculethat retain their covalent bonds during storage but, upon activation byan external energy source, form covalent bonds with other molecules.

Photoreactive groups generate active species such as free radicals andparticularly nitrenes, carbenes, and excited states of ketones uponabsorption of electromagnetic energy. Photoreactive groups can be chosento be responsive to various portions of the electromagnetic spectrum,and photoreactive species that are responsive to electromagneticradiation, including, but not limited to ultraviolet, infrared andvisible portions of the spectrum, are referred to as a “photochemicalgroup” or “photogroup.”

Free radical photoreactive groups can be classified by the following twotypes.

Type A. Compounds directly produce radicals by unimolecularfragmentation after light absorption. The radicals result from ahomolytic or heterolytic cleavage of a sigma bond inside the moleculeitself. Common examples include but are not limited to peroxides, andperoxy compounds, benzoin derivatives (including ketoxime esters ofbenzoin), acetophenone derivatives, benzilketals, α-hydroxyalkylphenonesand α-aminoalkylphenones, O-acyl α-oximinoketones, acylphosphine oxidesand acylphosphonates, thiobenzoic S-esters, azo and azide compounds,triazines and biimidazoles.

Type B. Compounds generate free radicals by bimolecular hydrogenabstraction after light absorption. The hydrogen abstractionphotoreactive group enters an excited state and undergo anintermolecular reaction with a hydrogen donor to generate free radicals.This leads to the formation of a pair of radicals originating from twodifferent molecules. The coupling of radicals can be used to formcrosslinks, especially in the solid state in the absence of solvents.Common examples include but are not limited to the following chemicalclasses. Quinones, benzophenones, xanthones and thioxanthones,ketocoumarins, aromatic 1,2 diketones and phenylglyoxylates. Hydrogenabstraction reactions can also occur intramolecularly. The reactions arenot effective for the direct initiation of polymerization and are usedinternally for the formation of an intermediate. This intermediate maybe effective for further cross linking depending on its structure.

Photoreactive crosslinkers are defined as multiphotofunctionalphotoreactive compounds containing a minimum of two photoreactive groupsthat can be homo- or hetero-functional. The photocrosslinkers undergoreactions with pre-existing polymer or oligomer chains to producecrosslinks, for example, a multiphotofunctional reactive compoundcontaining multiple benzophenone functionality. These photoreactivecrosslinkers are expected to be more efficient at creating covalentbonds within a matrix. Photocrosslinkers can also crosslink polymer tothe substrate surface and the surface of the particles to create a moredurable matrix.

The various photoreactive groups listed above can be incorporated intomoieties that have at least 2 (or more) of such photoreactive groups toafford photoreactive cross linking groups useful with the presentinvention. It should be understood that the photoreactive crosslinkermay contain two or more types of photoreactive groups.

Bis-azido benzylidene methylcyclohexanone, (ABC), (Structure X) is anexample of a multifunctional photocrosslinker based on phenyl azide thatis available from Aldrich Chemicals. Many heterodifunctional-initiatorscapable of cross linking through a photo and a non-photo initiatedmechanism are available from Pierce (Rockford, Ill.). Pierce supplies aphotoreactive crosslinker that is a homodifunctional-initiator,bis-[b-(4-azidosalicylamido)ethyl]disulfide.

The photolysis of organic azides has been shown to result in N₂ loss,producing nitrenes as reactive intermediates. Nitrenes are known toundergo five general reactions. 1) Addition to double bonds is observedfor both singlet and triplet nitrenes which in the case of arylnitrenesresults in rearrangement of the aziridine to a secondary amine as aconceivable mechanism. 2) Insertion of a nitrene into a carbon-hydrogenbond to give a secondary amine which is observed for singlet nitrenes.3) Hydrogen abstraction is the most common reaction of triplet nitrenesin solution where the formed amino radical and carbon radical generallydiffuse apart and the amino radical abstracts a second hydrogen atom togive a primary amine. 4) Nitrene dimerization 5) Attack on heteroatom,for example nitrenes react with azides and oxygen.

Eight commercially available multifunctional photocrosslinkers based ontrichloromethyl triazine are available either from Aldrich Chemicals,Produits Chimiques Auxiliaires et de Syntheses, (Longjumeau, France),Shin-Nakamara Chemical, Midori Chemicals Co., Ltd. or Panchim S. A.(France). The eight compounds include 2,4,6-tris(trichloromethyl)-1,3,5triazine, 2-(methyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,4-(4-carboxylphenyl)-2,6-bis(trichloromethyl)-1,3,5-triazine,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,2-(1-ethen-2-2′-furyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

For example,2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, (AldrichChemical) (Structure XI) is a type A photo initiator.

Upon direct excitation the homolytic cleavage of one of thecarbon-chlorine bonds occurs yielding a radical pair. The highlyreactive chlorine atom formed in this reaction abstracts a hydrogen atomto form a carbon radical and hydrogen chloride as shown in the followingScheme. The trichloromethyl triazine can serve as a photocrosslinkersince it contains two reactive groups.

The di-azide compound (Structure X) and the triazine compound (StructureXI) were evaluated in nanostructured surfaces and the coatings wereshown to have improved durability over coatings that did not contain aphotocrosslinker. (See Examples)

The use of photoreactive groups in the form of photoreactive arylketones are useful in photoreactive crosslinkers, such as acetophenone,benzophenone, anthraquinone, anthrone, and anthrone-like heterocycles(i.e., heterocyclic analogs of anthrone such as those having N, O, or Sin the 10-position), or their substituted (e.g., ring substituted)derivatives. Examples of aryl ketones include heterocyclic derivativesof anthrone, including acridone, xanthone, and thioxanthone, and theirring substituted derivatives. In particular, thioxanthone, and itsderivatives, having excitation energies greater than about 360 nm areuseful.

The photoreactive groups of such ketones are preferred since they arereadily capable of undergoing an activation/inactivation/reactivationcycle. Benzophenone, acetophenone and anthraquinone are examples ofphotoreactive moieties, since they are capable of photochemicalexcitation with the initial formation of an excited singlet state thatundergoes intersystem crossing to the triplet state. The excited tripletstate can insert into carbon-hydrogen bonds by abstraction of a hydrogenatom (from a support surface, for example), thus creating a radicalpair. Subsequent collapse of the radical pair leads to formation of anew carbon-carbon bond. If a reactive bond (e.g., carbon-hydrogen) isnot available for bonding, the ultraviolet light-induced excitation ofthe benzophenone, acetophenone or anthraquinone group is reversible andthe molecule returns to ground state energy level upon removal of theenergy source. Photoactivatible aryl ketones such as benzophenone,anthraquinone and acetophenone are of particular importance inasmuch asthese groups are subject to multiple reactivation in water and henceprovide increased coating efficiency.

The compositions of the invention can be applied to a surface ofinterest in any suitable manner. For example, the composition can beapplied by dip coating or by dispersing the compound on the surface (forexample, by spray coating). Suitable methods of application includeapplication in solution, dipping, spray coating, knife coating, androller coating. In one aspect, the compound is applied to the surfacevia spray coating, as this application method provides increased densityof the compound on the support surface, thereby improving durability.

Cross linking agents can be used in any suitable manner, including bythe simultaneous or sequential attachment of a chemical compound to asurface. Cross linking agents of the present invention can be used tomodify any suitable surface. Where the latent reactive group of theagent is a photoreactive group of the preferred type, it is particularlypreferred that the surface provide abstractable hydrogen atoms suitablefor covalent bonding with the activated group.

Plastics such as polyolefins, polystyrenes, poly(methyl)methacrylates,polyacrylonitriles, poly(vinylacetates), poly(vinyl alcohols),chlorine-containing polymers such as poly(vinyl)chloride,polyoxymethylenes, polycarbonates, polyamides, polyimides,polyurethanes, phenolics, amino-epoxy resins, polyesters, silicones,cellulose-based plastics, and rubber-like plastics can all be used assupports, providing surfaces that can be modified as described herein.See generally, “Plastics”, pp. 462-464, in Concise Encyclopedia ofPolymer Science and Engineering, Kroschwitz, ed., John Wiley and Sons,1990, the disclosure of which is incorporated herein by reference. Inaddition, supports such as those formed of pyrolytic carbon, parylenecoated surfaces, and silylated surfaces of glass, ceramic, or metal aresuitable for surface modification.

Cross linking compounds encompassed by the present invention can beprepared by selection of an appropriate aryl group with aphotoactivatable group and at least one group that can either act as anucleophilic site or can be acted upon in a nucleophilic displacementreaction with a linking agent (L) having at least two opposing groups,either a leaving group(s) or a nucleophilic group(s). General syntheticschemes detailed below demonstrate two approaches suitable to preparecompounds of the invention.

or

wherein X is an integer equivalent to “n” and n is an integer between 2and about 6, R³and R⁴ are as defined above, “Y” is a leaving group or agroup that can be acted upon by a nucleophilic group, such as an ester,carboxylic acid halide, etc. and “Nuc” is a nucleophilic group, asdescribed in further detail below. Alternatively, the reaction between“Y” and “Nuc” can be a condensation reaction, such as the reactionbetween, for example, a hydroxyl group and a carboxylic acid.

It should be understood in schemes I and II, that R³ and R⁴ areinterchangeable.

Suitable nucleophilic groups (Nuc) include, for example, amines,hydroxyl, thiol, etc.

Suitable leaving groups, or groups susceptible to nucleophilic attack,include esters, ethers, epoxides, halides, isocyanates, isothiocyanates,sulfonyl chlorides, anhydrides, carboxylic acid halides, carboxylic acidesters, and aldehydes.

Resultant functional moieties from the reaction between the nucleophilicgroup and leaving (or condensation group) include, for example, esters,ethers, carbamates, thiocarbamates, sulfones, amides, ureas, thiourea,amines, sulfonamides, imines (that can be further reduced with areducing agent such as sodium borohydride to an amine), etc.

Suitable reaction conditions for such condensations or nucleophilicdisplacements are known in the art. For example, hydroxyl containingmoieties can be condensed with a carboxylic acid under dehydratingconditions (refluxing toluene, acid catalyst, Dean Stark trap) to formesters. Reactive halides can be displaced by hydroxyl groups under basicconditions. An isocyanate reacts with a hydroxyl group with heat to formcarbamates. Likewise, an isothiocyanates reacts with a hydroxyl group toform a thiocarbamate. Under deprotonation conditions, a hydroxide ionreacts with an epoxide to form an ether linkage and forming a newhydroxyl group. Reaction between a hydroxyl and a sulfonyl chlorideforms a sulfone. Reaction between a hydroxyl and an anhydride will forma ester with a carboxylic acid portion as well. Reaction between ahydroxyl group and an ester will also form an ester, with the removal ofa corresponding displaced alcohol, generally under conditions that driveoff the displaced alcohol.

Much like the reactions with hydroxyl groups, amines serve in similarmanner. For example, an amine can react with an activated carboxylicacid for form an amide. Activation of a carboxylic acid can befacilitated by various methods in the art, including for example, use ofdicyclohexylcarbodiimide (DCC) that generates urea as a side product. Anisocyanate reacts with an amine to form a urea and an isothiocyanatereacts with an amine to form a thiourea.

Reaction between an amine and an epoxide will form an amine with anappended hydroxyl group from the nucleophilic displacement of theepoxide ring. Reaction between an amine and a sulfonyl chloride willform a sulfonamide. Reaction between an anhydride and an amine willafford an amide with a carboxylic portion attached to the product.Reaction between an aldehyde and an amine will form an imine which canbe further reduced to an amine. Reaction between a carboxylic acidhalide and an amine will form an amide, as well as the reaction betweena carboxylic ester and amine. Lastly, melamine type compounds can reactwith an amine to form amine linkages.

Reaction conditions to form the compounds of the invention are known inthe art. For example, suitable reaction conditions are described in“March's Advanced Organic Chemistry: Reactions, Mechanisms, andStructure, 5th Edition, John Wiley & Sons, Michael B. Smith & JerryMarch; Fieser and Fieser's Reagents for Organic Synthesis” John Wiley &Sons, NY; Vogel's Textbook of Practical Organic Chemistry (FifthEdition) by A. I. Vogel, B. S. Furniss, A. J. Hannaford, P. W. G. Smith,and A. R. Tatchell, Longman Scientific and Technical, Longman Group UK;and Advanced Organic Chemistry parts A and B″ Third Edition, F. A.Carey, R. S. Sundberg, Plenum Press, NY, 1990, the contents of which areincorporated herein by reference in their entirety.

It should also be understood that each “Y” independently can bedifferent. Therefore, it is possible to have reaction products thatinclude an ether linkage as well as an ester linkage to the carbonylcontaining photoactivatable group.

An exemplary non-limiting reaction is depicted in Scheme III, in which ahydroxyl group undergoes nucleophilic addition to an ester or acidhalide or can undergo a condensation reaction between the hydroxyl groupand a carboxylic acid.

A second class of photocrosslinkers that undergo 2+2 cycloadditions whenphotolyzed can be synthesized with the following general scheme.

X, Y, and Z are functional groups described above as nucleophiles andleaving groups. R1 is typically substituted or unsubstituted aryl orcontains substituted allylic groups or carbonyl groups which areconjugated with the main alkene. R3 is a substituted aryl or alkylsubstituent which may include other functionalities such as esters,amides, ethers, etc. R2 is any linking agent, such as those shown above.Similarly, the X group may reside on the R1 component instead of the R3,giving additional photocrosslinkers.

In some cases, one arm of the photocrosslinker will be as the abovealkene and one arm will be from the aryl ketone scheme described above.This may be particularly advantageous because alkene 2+2 photochemistrygenerally requires an additional alkene from the polymer or substratefor reaction. If a crosslinker with one alkene and one benzophenone wasused, the benzophenone would be available for broad coupling to thepolymer, while the alkene would be available for the more specificcoupling of alkene to alkene on two crosslinkers, thus crosslinking thepolymer matrix.

Other classes of photocrosslinkers include azides,trichloromethyl-substituted compounds and peroxides. A method tosynthesize the bis(trichloromethyl)-1,3,5-triazine crosslinkers thatcontain multiple triazine groups could include of the use of4-(4-carboxylphenyl)-2,6-bis-(trichloromethy)-1,3,5-triazine which canbe converted to the acid chloride and reacted with a linker, asdescribed throughout.

Many methods to synthesize multifunctional azide type crosslinkers arepossible. Alkyl azides are best prepared by nucleophilic displacement onalkyl halides using sodium azide. Other ways to prepare azides includereactions between hydrazines and nitrous acid, reactions of amine anionswith tosyl azide, reactions of diazonium salts with sodium azide andsubstitution reactions with compounds containing a double bond. For thesynthesis of multifunctional azide containing reagents the conversion tothe azide would generally be the last step in the synthetic schemeutilizing a bifunctional or multifunctional reagent.

The synthesis of multifunctional peroxide type crosslinkers containingdiacyl peroxides and acyl hydroperoxides can be prepared from compoundscontaining multiple functional groups such as carboxylic acids, acylhalides, or anhydrides. Mixed alkyl-acyl peroxides, (peresters) can beprepared from acyl halides and hydroperoxides, or through reaction of anacid and hydroperoxide with DCC. As with the multifunctional azide typecrosslinkers, the formation of the peroxide would generally be the laststep in the synthetic scheme. Multifunctional acids could serve as thecore linker.

Suitable polymers useful in combination with the crosslinkers notedthroughout the specification include those described in U.S. Pat. No.6,683,126, issued Jan. 27, 2004 to Keller et al., described as binders,the contents of which are included herein in their entirety.

As described above, the particle can be virtually any type of particlethat has a particle size of between about 1 nm and about 25 microns andup to 1000 nm). The particle can be porous or non-porous. Generally, theparticle has an oxide layer but in particular has been treated with asilane reagent to provide hydrophobicity. Suitable materials include,but are not limited to, particles derived from aluminum oxides(alumina), titanium oxide, zirconium oxide, gold (treated with thiols),silver (thiol or silane treated), nickel, iron oxide, and alloys (alltreated with silane), polystyrene particles, (meth)acrylates particles,PTFE particles, silica particles, polyolefin particles, polycarbonateparticles, polysiloxane particles, silicone particles, polyesterparticles, polyamide particles, polyurethane particles, ethylenicallyunsaturated polymer particles, polyanhydride particles and biodegradableparticles such as polycaprolactone (PCL) and polylactideglycolide(PLGA), and nanofibers, nanotubes, or nanowires and combinationsthereof.

The particles may also be used to give properties to the surface otherthan hydrophobicity. For example, inclusion of silver particles may giveanti-bacterial properties to the surface. Silver has long been known tohave broad spectrum antimicrobial properties. The silver cation binds tothiols and other groups, denaturing proteins. When bound to proteins inthe bacterial cell wall, rupture can ensue, killing the bacteria. Silvermay also bind respiratory enzymes and DNA leading to further cell death.Its use in the particle aspect of these matrices may provide additionalbenefits beyond texture. Similarly, gold nanoparticles may give effectscommon to gold nanoparticles such as fluorescence quenching or surfaceplasmon resonance. Polymer matrix coatings may be tailored with theseadditional features in mind.

As noted throughout the specification, the particle can be pretreatedwith a silane to help increase hydrophobicity of the ultimatecomposition. Silanation of surfaces is known in the art. Generally, anyhydrophobic silane that can react with a surface can be used with theparticles described herein

For example, Cab-O-Sil TS 720 (Cabot, a silica product, uses a dimethylsilicone (polydimethylsiloxane) according to the MSDS. Other silanatingagents used on Cab-O-Sil products include hexamethyldisilazane anddichlorodimethylsilane. Similar silica products are available fromDegussa (www.degussa.com, Duesseldorf, Germany), under their Aerosil Rand LE lines that are silanated with various silane reagents, includingoctamethylcyclotetrasiloxane.

Not to be limited by the following, it is possible to treat uncoatedparticles using a solution phase reaction. A long chain alkanesilane,such as octadecyltrichlorosilane, decyltrichlorosilane, etc. can beused. The chain length can be varied from about 1 to 20, though the 18is very common. Additionally there are aryl silanes, such astolyldimethylchlorosilane, phenyltrichlorosilane, etc. andfluoroalkylsilanes like heptadecafluorodecyltrichlorosilane(fluorosilanes) having the same chain length range as straight alkylchains, with complete or almost complete fluorination.

The silanes react with the particle surface through reactive groups,such as chloro groups (mono, di, and tri-chloro) or through alkoxygroups (mono-methoxy, di-methoxy, trimethoxy or ethoxy versionstypically). They can have one, two, or three chains, though it is morecommon to have one chain, and one or two methyl groups. Such silanes aresold commercially from Gelest Inc., Morrisville, Pa. www.gelest.com.Application procedures are found in the Gelest catalog, the contents ofwhich are incorporated herein by reference

Typically, to treat a particle with a chlorosilane, a 1-5 wt % solutionis prepared in anhydrous alcohol or acetone solution. The particles areadded in the same solvent, and mixed until HCl production is completed.Alkoxy silanes can be applied in a solution of 95:5 ethanol:water at pH4-5. The silane is applied to the particles generally at a 2%concentration, stirred for a period of time, and the solvent removed.Generally, pretreated “silanated” particles are commercially available.

Any type of silica particle can be used in the compositions of theinvention. The silica can be porous or non-porous and in particular canbe treated with a silane to help improve hydrophobicity. Suitable silicaparticles are included as described in U.S. Pat. No. 6,683,126, thecontents of which are included herein in their entirety.

In a first embodiment, the present invention pertains to a compositioncomprising a cross linking compound comprising a formula:

L-((D-T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m)

wherein L is a linking group;

D is O, S, SO, SO₂, NR⁵ or CR⁶R⁷;

T is (—CH₂—)_(x), (—CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond;

R¹ is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl oraryloxyaryl group;

X is O, S, or NR⁸R⁹;

P is a hydrogen atom or a protecting group, with the provisio that P isabsent when X is NR⁸R⁹;

R² is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl oraryloxyaryl group;

G is O, S, SO, SO₂, NR¹⁰, (CH₂)_(t)—O— or C═O;

R³ and R⁴ are each independently an alkyl, aryl, arylalkyl, heteroaryl,or an heteroarylalkyl group or, optionally, R³ and R⁴ can be tetheredtogether via (—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s),(—CH₂—)_(r)S(—CH₂—)_(s), (—CH₂—)_(r)S═O(—CH₂—)_(s) or(—CH₂—)_(r)S(O)₂(—CH₂—)_(s), (—CH₂—)_(r)NR(—CH₂—)_(s);

R⁵ and R¹⁰ are each independently a hydrogen atom or an alkyl, aryl orarylalkyl group;

R⁶ and R⁷ are each independently a hydrogen atom, an alkyl, aryl,arylalkyl, heteroaryl or heteroarylalkyl group;

R⁸ and R⁹ are each independently a hydrogen atom, an alkyl, aryl, orarylalkyl group;

R is a hydrogen atom, an alkyl or an aryl group;

q is an integer from 1 to about 7;

r is an integer from 0 to about 3;

s is an integer from 0 to about 3;

m is an integer from 2 to about 10;

t is an integer from 1 to about 10;

x is an integer from 1 to about 500;

a polymer; and

a particle having a particle size of between about 1 nm to about 25microns.

In a second embodiment of the first embodiment, L is a branched orunbranched alkyl chain having between about 2 and about 10 carbon atoms.

In a third embodiment of either of the first or second embodiments, D isO.

In a fourth embodiment of any of the first through third embodiments, Tis (—CH₂—)_(x) or (—CH₂CH₂—O—)_(x) and x is 1 or 2.

In a fifth embodiment of the any of the first through fourthembodiments, R¹ is a hydrogen atom.

In a sixth embodiment of any of the first through fifth embodiments, Xis O and P is a hydrogen atom.

In a seventh embodiment of any of the first through the sixthembodiments, R² is a hydrogen atom.

In an eighth embodiment of any of the first through the seventhembodiments, G is O.

In a ninth embodiment of any of the first through the eighthembodiments, R³ and R⁴ are each individually aryl groups.

In a tenth embodiment of any of the first through the ninth embodiments,m is 3.

In an eleventh embodiment of the first embodiment, L is

D is O, T is (—CH₂—)_(x), R¹ is a hydrogen atom, X is O, P is a hydrogenatom, R² is a hydrogen atom, G is O, R³ and R⁴ are phenyl groups, m is 3and x is 1.

In a twelfth embodiment of the first embodiment, L is (—CH₂—)_(y), D isO, T is (—CH₂—)_(x), R¹ is a hydrogen atom, X is O, P is a hydrogenatom, R² is a hydrogen atom, G is O, R³ and R⁴ are phenyl groups, m is2, x is 1 and y is an integer from 2 to about 6.

In a thirteenth embodiment of the twelfth embodiment, y is 2, 4 or 6.

In a fourteenth embodiment, the present invention pertains to acomposition comprising a cross linking compound comprising a formula:

L-((T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m)

wherein L, T, R¹, X, R⁸, R⁹, P (with the provisio that P is absent whenX is NR⁸R⁹), R², G, R³, R⁴, R¹⁰, R, q, r, s, m, t, and x are as definedabove.

In a fifteenth embodiment of the fourteenth embodiment L has a formulaaccording to structure (I):

wherein A and J are each independently a hydrogen atom, an alkyl group,an aryl group, or together with B form a cyclic ring, provided when Aand J are each independently a hydrogen atom, an alkyl group, or an arylgroup then B is not present;

B is NR¹¹, O, or (—CH₂—)_(z);

provided when A, B and J form a ring, then A and J are (—CH₂—)_(z) orC═O;

R¹¹ is a hydrogen atom, an alkyl group, an aryl group or denotes a bondwith T;

each z independently is an integer from 0 to 3;

provided when either A or J is C═O, then B is NR¹¹, O, or (—CH₂—)_(z)and z must be at least 1;

a polymer; and

a particle having a particle size of between about 1 nm to about 25microns.

In a sixteenth embodiment of either the fourteenth or fifteenthembodiments, T is —CH₂—.

In a seventeenth embodiment of any of the fourteenth through sixteenthembodiments, R¹ is a hydrogen atom.

In an eighteenth embodiment of any of the fourteenth through seventeenthembodiments, X is O and P is a hydrogen atom.

In a nineteenth embodiment of any of the fourteenth through eighteenthembodiments, R² is a hydrogen atom.

In a twentieth embodiment of any of the fourteenth through nineteenthembodiments, G is O.

In a twenty first embodiment of any of the fourteenth through twentiethembodiments, R³ and R⁴ are each individually aryl groups.

In a twenty second embodiment of any of the fourteenth through twentyfirst embodiments, m is 3.

In a twenty third embodiment of the fifteenth embodiment, A and J areboth C═O and B is N.

In a twenty fourth embodiment of the fifteenth embodiment, A and J areboth hydrogen atoms.

In a twenty fifth embodiment, the present invention pertains to acomposition comprising a cross liking compound comprising a formula:

L-((GTZR³C(═O)R⁴))_(m)

wherein Z is C═O, COO, or CONH when T (—CH₂—)_(x);

L, T, G, R³, R⁴, R¹⁰, R, q, r, s, m, t, and x are as defined above;

a polymer; and

a particle having a particle size of between about 1 nm to about 25microns.

In a twenty sixth embodiment of the twenty fifth embodiment, L has theformula according to structure (I) as defined above.

In a twenty seventh embodiment of either the twenty fifth or twentysixth embodiments, T is —CH₂—.

In a twenty eighth embodiment of any of the twenty fifth through thetwenty seventh embodiments, G is O.

In a twenty ninth embodiment of any of the twenty fifth through twentyeighth embodiments, R³ and R⁴ are each individually aryl groups.

In a thirtieth embodiment of any of the twenty fifth through twentyninth embodiments, wherein m is 2.

In a thirty first embodiment of any of the twenty sixth throughthirtieth embodiments, A and J are both C═O and B is NR¹¹.

In a thirty second embodiment of the twenty sixth embodiment, A and Jare both hydrogen atoms.

In a thirty third embodiment of the twenty fifth embodiment, L has aformula according to structure (II):

wherein R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are each independently a hydrogenatom, an alkyl or aryl group or denotes a bond with T, provided at leasttwo of R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ are bonded with T and each K,independently, is CH or N.

In a thirty fourth embodiment of the twenty fifth embodiment, L is C═O.

In a thirty fifth embodiment of the thirty fourth embodiment, G is NH.

In a thirty sixth embodiment of either the thirty fourth or thirty fifthembodiments, T is —CH₂CH₂O—.

In a thirty seventh embodiment of any of the thirty fourth throughthirty sixth embodiments, Z is C═O.

In a thirty eighty embodiment of any of the thirty fourth through thirtyseventh embodiments, R³ is an aryl group.

In a thirty ninth embodiment of any of the thirty fourth through thirtyeighth embodiments, R⁴ is an aryl group.

In a fortieth embodiment, the present invention pertains to acomposition comprising a cross linking compound comprising a formula:

L-((TGQR³C(═O)R⁴))_(m)

wherein L, T, G, R³, R³, R⁴, R¹⁰, R, q, r, s, m, t and x are as definedabove and Q is (—CH₂—)_(p), (—CH₂CH₂—O—)_(p), (—CH₂CH₂CH₂—O—)_(p) or(—CH₂CH₂CH₂CH₂—O—)p and p is an integer from 1 to about 10;

a polymer; and

a particle having a particle size of between about 1 nm to about 25microns.

In a forty first embodiment of the fortieth embodiment, L has theformula according to structure (I) as defined above.

In a forty second embodiment if either the fortieth or forty firstembodiments, T is —CH₂—.

In a forty third embodiment of any of the fortieth through forty secondembodiments, G is O.

In a forty fourth embodiment of any of the fortieth through the fortythird embodiments, R³ and R⁴ are each individually aryl groups.

In a forty fifth embodiment of any of the fortieth through forty fourthembodiments, m is 2.

In a forty sixth embodiment of any of the forty first through fortyfifth embodiments, A and J are both C═O and B is NR¹¹.

In a forty seventh embodiment of any of the forty first through fortyfifth embodiments, A and J are both hydrogen atoms.

In a forty eighth embodiment of the fortieth embodiment, L has theformula according to structure (II) as defined above.

In a forty ninth embodiment, the present invention pertains to acomposition comprising a cross linking compound comprising a formula:

L-((-CH₂—)_(xx)C(R¹)(GR³C(═O)R⁴)₂)_(m)

wherein L, R¹, G, R³, R⁴, R¹⁰, R, q, r, s, m, t are as defined above andxx is an integer from 1 to about 10;

a polymer; and

a particle having a particle size of between about 1 nm to about 25microns.

In a fiftieth embodiment of the forty ninth embodiment, L has theformula according to structure (I) as defined above.

In a fifty first embodiment of the fiftieth embodiment, A and J are bothhydrogen atoms.

In a fifty second embodiment of any of the forty ninth through fiftyfirst embodiments, wherein xx is 1.

In a fifty third embodiment of any of the forty ninth through fiftysecond embodiment, wherein each R¹ is H.

In a fifty fourth embodiment of any of the forty ninth through fiftythird embodiments, wherein each G is (—CH₂—)_(t)O— and t is 1.

In a fifty fifth embodiment of any of the forty ninth through fiftyfourth embodiments, each R³ and R⁴ are each individually aryl groups.

In a fifty sixth embodiment of any of the forty ninth through fiftyfifth embodiments, wherein xx is 1, each G is (—CH₂—)_(t)O— and t is 1,each R¹ is H and each R³ and R⁴ are each individually aryl groups.

In a fifty seventh embodiment, the present invention pertains to acomposition comprising a cross linking compound comprising the formula:

L-((-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m)

wherein L, R', X, P, R⁸, R⁹, R², R¹⁰, G, R³, R³, R⁴, R, q, r, s, m and tare as defined as above;

a polymer; and

a particle having a particle size of between about 1 nm to about 25microns.

In a fifty eighty embodiment of the fifty seventh embodiment, L is

and R²⁰ and R²¹ are each individually a hydrogen atom, an alkyl group oran aryl group.

In a fifty ninth embodiment of either the fifty seventh or fifty eighthembodiments, wherein R¹ is H.

In a sixtieth embodiment of any of the fifty seventh through fifty ninthembodiments, wherein X is O.

In a sixty first embodiment of any of the fifty seventh through sixtiethembodiments, P is H.

In a sixty second embodiment of any of the fifty seventh through sixtyfirst embodiments, R² is H.

In a sixty third embodiment of any of the fifty seventh through sixtysecond embodiments, G is (—CH₂—)_(t)O— and t is 1.

In a sixty fourth embodiment of any of the fifty seventh through sixtythird embodiments, R³ and R⁴ are each individually aryl groups.

In a sixty fifth embodiment of the fifty eight embodiment, R¹ is H, X isO, P is H, R² is H, G is (—CH₂—)_(t)O—, t is 1, R³ and R⁴ are eachindividually aryl groups and R²⁰ and R²¹ are both methyl groups.

In a sixty sixth embodiment, the present invention pertains to acomposition comprising a cross linking compound comprising the formula:

L-((GR³C(═O)R⁴))_(m);

wherein L, G, R³, R⁴, R¹⁰, R, q, r, s, m and t are as defined above;

a polymer; and

a particle having a particle size of between about 1 nm to about 25microns.

In a sixty seventh embodiment, L is

In a sixty eighth embodiment of either the sixty sixth or sixty seventhembodiments, G is C═O.

In a sixty ninth embodiment of any of sixty sixth through sixty eighthembodiments, R³ and R⁴ are each individually aryl groups.

In a seventieth embodiment of any of the sixty sixth through sixty ninthembodiments, G is C═O and R³ and R⁴ are each individually aryl groups.

In a seventy first embodiment, the present invention pertains to acomposition comprising a cross linking compound comprising a formula:

L-((ZZ-D-T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m)

wherein L, D, T, R¹, R⁵, R⁶, R⁷, T, X, P, N⁸, N⁹, R², G, R¹⁰, R³, R⁴, R,q, r, s, m, t, x are as defined above;

ZZ is a phenyl group;

a polymer; and

a particle having a particle size of between about 1 nm to about 25microns.

In a seventy second embodiment of the seventy first embodiment, m is 3.

In a seventy third embodiment of the seventy first or seventy secondembodiments, L is CH.

In a seventy fourth embodiment of the seventy first embodiment, L is CH,ZZ is phenyl, D is O, T is CH₂, R¹ is H, P is H, R² is H, G is O, R³ isphenyl, R⁴ is phenyl substituted with a —OC_(8H) ₁₇ and m is 3.

In a seventy fifth embodiment of any of the first through seventy fourthembodiments, R³ and R⁴ are both phenyl groups and are tethered togethervia a CO, a S or a CH₂.

In a seventy sixth embodiment of any of the first through seventy fourthembodiments, R³ and R⁴ are both phenyl groups and include at least oneCH₃OCH₂CH₂O—.

In a seventy seventh embodiment of any of the first through seventyfourth embodiments, the particle is a porous or non-porous particlecomprising aluminum oxides (alumina), titanium oxide, zirconium oxide,gold (treated with thiols), silver (thiol or silane treated), nickel,iron oxide, and alloys (all treated with silane), polystyrene particles,(meth)acrylates particles, PTFE particles, silica particles, polyolefinparticles, polycarbonate particles, polysiloxane particles, siliconeparticles, polyester particles, polyamide particles, polyurethaneparticles, ethylenically unsaturated polymer particles, polyanhydrideparticles and biodegradable particles such as polycaprolactone (PCL) andpolylactideglycolide (PLGA), and nanofibers, nanotubes, or nanowires,and combinations thereof.

In a seventy eighth embodiment of any of the first through seventyseventh embodiments, the particle is pretreated with a silane.

In a seventy ninth embodiment, the present invention pertains to amethod to modify a substrate comprising the step of applying acomposition of any of claims first through seventy eighth embodiments tothe surface, such that the substrate surface is modified.

In an eightieth embodiment, the method of the seventy ninth embodimentis photoactivated such that at least one photoactivatable group withinthe composition forms a covalent bond with the surface of the substrate.

In an eighty first embodiment, the method of the seventy ninthembodiment is photoactivated such that a coating is formed frominterpolymer cross linking.

In an eighty second embodiment, the present invention pertains to asuper hydrophobic composition comprising a photoreactive cross linkingcompound, a polymer and a particle having a particle size of betweenabout 1 nm to 25 microns. The cross linking compound is any of thosedescribed in any of the first through seventy eighth embodiments.

In an eighty third embodiment of the eighty second embodiment, thephotoreactive moiety of the cross linking compound is selected from thegroup consisting of benzoin derivatives (including ketoxime esters ofbenzoin), acetophenone derivatives, benzilketals,α-hydroxyalkylphenones, α-aminoalkylphenones, O-acyl α-oximinoketones,acylphosphine oxides, acylphosphonates, thiobenzoic S-esters, azo, azidecompounds, triazines, biimidazoles , quinones, benzophenones, xanthonesand thioxanthones, coumarins, aromatic 1,2 diketones, peroxides,trichloromethyl substituted compounds, aryl ketones, phenyl glyoxylateand 2+2 photogroups.

In an eighty fourth embodiment, the present invention pertains to anultra hydrophobic composition comprising a photoreactive cross linkingcompound, a polymer and a particle having a particle size of betweenabout 1 nm to 25 microns.

In an eighty fifth embodiment fo the eighty fourth embodiment, thephotoreactive moiety of the cross linking compound is selected from thegroup consisting of benzoin derivatives (including ketoxime esters ofbenzoin), acetophenone derivatives, benzilketals,α-hydroxyalkylphenones, α-aminoalkylphenones, O-acyl α-oximinoketones,acylphosphine oxides, acylphosphonates, thiobenzoic S-esters, azo, azidecompounds, triazines, biimidazoles, quinones, benzophenones, xanthonesand thioxanthones, coumarins, aromatic 1,2 diketones, peroxides,trichloromethyl substituted compounds, aryl ketones and 2+2 photogroups.

The invention will be further described with reference to the followingnon-limiting Examples. It will be apparent to those skilled in the artthat many changes can be made in the embodiments described withoutdeparting from the scope of the present invention. Thus the scope of thepresent invention should not be limited to the embodiments described inthis application, but only by embodiments described by the language ofthe claims and the equivalents of those embodiments. Unless otherwiseindicated, all percentages are by weight.

Example 1 Synthesis of Trifunctional Triazine Crosslinker

1.2 g (4 mmol) of triglycidyl isocyanurate (Aldrich Chemicals,Milwaukee, Wis.) and 2.4 g (12 mmol) of 4-hydroxybenzophenone (AldrichChemicals, Milwaukee, Wis.) were mixed in a 50-ml round bottom flaskcontaining a magnetic stir bar. The flask was flushed with argon for 10min and heated to 130° C. in an oil bath. Once the reaction mixturemelted, 6 mg (0.02 mmol) of triphenylphosphine (Aldrich Chemicals,Milwaukee, Wis.) was added. The mixture was stirred for another 2minutes under argon and cooled to room temperature. The reaction residuewas dissolved in 30 ml chloroform, then washed with 4N NaOH (30 ml×3)and deionized water (30 ml×3). The organic layer was dried overmagnesium sulfate and concentrated to dryness on the under reducedpressure. The product was purified by column chromatography (silica gel,230-400 mesh, Whatman, Inc.) using ethyl acetate as eluent (R_(f)˜4.5).The fractions containing the pure product were combined and concentratedunder reduced pressure and a white powder was obtained after dryingunder vacuum (yield 70%).

The crosslinker is soluble in most common solvents including chloroform,methylene chloride, acetone, ethyl acetate, isopropanol, etc. ¹H NMR(CDCl₃) confirmed the structure of the product. The peaks at d 7.78 ppm(m, 12H), 7.46 ppm (m, 9H), 6.98 ppm (m, 6H) were the typical signalsfrom 4-subsituted benzophenone. The peak at d 4.35 ppm (m, 6H) wasassigned to the protons of methylene connected to phenoxy group. Thepeak at d 4.13 ppm (m, 9H) was a combination of 6 protons of 3 methylenegroups connected to nitrogen atom and 3 protons from 3 methine groups.The peak at d 3.00 ppm (s, 3H) corresponded to hydroxyl groups.

Example 2 Application of Triazine Crosslinker to Create a PhotoreactiveSurface

A photoreactive poly(ε-caprolactone) (PCL) film was prepared byincorporating the crosslinker in a film casting polymer solution. Asolution containing 20 mg/ml PCL (Aldrich Chemicals, Milwaukee, Wis.)and 0.4 mg/ml triazine crosslinker (as prepared in Example 1) was castonto a glass slide. 10 μl of 50 mg/ml poly(vinylpyrrolidone) (PVP, 30K,Kollidon K30 BASF, NJ) in isopropanol solution was added onto the film.After complete evaporation of the isopropanol, the film was illuminatedunder UV for 20 minutes (UV Crosslinker, UVP CL-1000, Upland, Calif.,254 nm light, 120,000 μJ/cm²). The coated film was incubated indeionized water on a shaker for 3 hours to remove unbound PVP. Ahomogeneous PVP coating could be seen on the PCL film by staining with asolution of Congo Red (0.5% w/v aqueous solution) indicating a uniformdistribution of crosslinker on the film surface. A PCL film withouttriazine crosslinker added showed no staining, indicating all unboundPVP was removed by the rinse.

Example 3 Synthesis of Photoreactive Glycol Crosslinker

2.26 g 4-hydroxybenzophenone (Aldrich Chemicals, Milwaukee, Wis.) wasdissolved in 50 ml of acetone, and 0.532 ml of glycerol triglycidylether (Polysciences, Warrington, Pa.), and 3.3 g potassium carbonate(Aldrich Chemicals, Milwaukee, Wis.) were added to the solution. Thereaction mixture was heated to reflux over 24 hours. After 24 hours ofheating, thin layer chromatography (TLC) showed consumption of theglycerol starting material (eluent 20:1 Chloroform:methanol) and theemergence of three uv active spots. The acetone was removed by rotaryevaporation and the residue was dissolved in chloroform, and filtered.The resulting chloroform solution was washed three times with 4N NaOHaqueous solution, once with deionized water, then twice with 1N HClaqueous solution, and three times again with deionized water. Thechloroform solution was dried over magnesium sulfate, filtered, and thesolvent removed by rotary evaporation. The resulting oil was washedthree times with diethyl ether and dried. This treatment removed all4-hydroxybenzophenone starting material, with TLC revealing the samethree uv active spots. These three products presumably correspond tosingle, double, and triple substitution of benzophenone on the glycerolcompound.

Coating Composition A

320 mg of polycaprolactone (Aldrich Chemicals, Milwaukee, Wis.,Mn=80,000) and 13 mg triazine crosslinker (Example 1) were dissolved in20 ml methylene chloride. 330 mg of CAB-O-SIL® TS-720 silicananoparticles (Cabot Corp. Tuscola, Ill.) were dispersed in the solutionwith intensive vortexing. The coating composition was sprayed on a LNBsurface (provided by King Controls, Bloomington, Minn.) using acommercial hair spray. After the solvent evaporated, the LNB wasirradiated under UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt, 254nm, 10 cm from light source) for 20 min.

Coating Composition B

160 mg of polybutyl methacrylate (Aldrich Chemicals, Milwaukee, Wis.,Mw=337,000), 160 mg of polycaprolactone (Aldrich Chemicals, Milwaukee,Wis., Mn=80,000) and 13 mg triazine crosslinker (Example 1) weredissolved in 20 ml methylene chloride. 330 mg of CAB-O-SIL® TS-720silica nanoparticles (Cabot Corp. Tuscola, Ill.) were dispersed in thesolution with intensive vortexing. The coating composition was sprayedon a LNB surface (provided by King Controls, Bloomington, Minn.) using acommercial hair spray. After the solvent evaporated, the LNB wasirradiated under UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt, 254nm, 10 cm from light source) for 20 min.

Coating Composition C

150 mg of polystyrene (Aldrich Chemicals, Milwaukee, Wis., Mw=280,000)and 30 mg triazine crosslinker (Example 1) were dissolved in 20 mlmethylene chloride. 250 mg of CAB-O-SIL® TS-720 silica nanoparticles(Cabot Corp. Tuscola, Ill.) were dispersed in the solution withintensive vortexing. The coating composition was sprayed on a LNBsurface (provided by King Controls, Bloomington, Minn.) using acommercial hair spray. After the solvent evaporated, the LNB wasirradiated under UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt, 254nm, 10 cm from light source) for 20 min.

Coating Composition D

200 mg of polystyrene (Aldrich Chemicals, Milwaukee, Wis., Mw=280,000)and 40 mg triazine crosslinker (Example 1) were dissolved in 20 mlmethylene chloride. 250 mg of CAB-O-SIL® TS-720 silica nanoparticles(Cabot Corp. Tuscola, Ill.) were dispersed in the solution withintensive vortexing. The coating composition was sprayed on a LNBsurface (provided by King Controls, Bloomington, Minn.) using acommercial hair spray. After the solvent evaporated, the LNB wasirradiated under UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt, 254nm, 10 cm from light source) for 20 min.

Coating Composition E

130 mg of polyisobutylene (Aldrich Chemicals, Milwaukee, Wis.,Mw=500,000) and 6 mg triazine crosslinker were dissolved in 20 ml THF.156 mg of CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola,Ill.) were dispersed in the solution with intensive vortex mixing. Thecoating composition was sprayed on a LNB surface (provided by KingControls, Bloomington, Minn.) using a commercial hair spray. After thesolvent evaporated, the LNB was irradiated under UV (UVP CL-1000Ultraviolet Crosslinker, 40 watt, 254 nm, 10 cm from light source) for20 min.

Coating Composition F

133 mg of polyisobutylene (BASF Corp. Florham Park, N.J., Mw=2,000,000)and 6 mg triazine crosslinker were dissolved in 120 ml THF. 160 mg ofCAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.) weredispersed in the solution with intensive vortex mixing. The coatingcomposition was sprayed on a LNB surface (provided by King Controls,Bloomington, Minn.) using a commercial hair spray. After the solventevaporated, the LNB was irradiated under UV (UVP CL-1000 UltravioletCrosslinker, 40 watt, 254 nm, 10 cm from light source) for 20 min.

Super Hydrophobicity Test

Coatings A, B, C, D, E and F showed comparable super hydrophobicity to acommercial super hydrophobic coating product—King's Rain Shield (KingControls, Bloomington, Minn.) with water contact angles higher than150°. Water drops could hardly sit on the coatings.

Coating Durability Test

The durability of coatings A, B, C, D, E and F all showed improveddurability against rub, touch and water flow compared to King's RainShield.

A three-month weather stability study was conducted using satellite dishLNBs provided by King Controls, Inc. The LNBs were spray coated using aformulation containing 20 mg/mL of polycaprolactone (Aldrich Chemicals,Milwaukee, Wis., Mw=80,000), 240 mg/mL CAB-O-SIL® TS-720 silicananoparticles (Cabot Corp. Tuscola, Ill.), 0.8 mg/mL triazinecrosslinker in THF, allowed to evaporate, and then irradiated withultraviolet light (300 to 400 nm) for 5 minutes (Harland Medical UVM400,Eden Prairie, Minn.). Three LNBs were coated with a commercial waterrepellent product (King's Rain Shield, King Controls, Inc., Bloomington,Minn.) as control. The coated samples and controls were placed outdoorsfor weather exposure. At regular intervals the sample LNBs were testedusing several drops of DI water to determine super hydrophobicity of thecoated surface. The results showed that after eight days the commercialcoatings lost super hydrophobicity whereas PCL/nanoparticle/triazinecrosslinker coatings remained super hydrophobic for greater than threemonths.

Example 4 Synthesis of Photoreactive Glycol Crosslinker

2.26 g 4-hydroxybenzophenone (Aldrich Chemicals, Milwaukee, Wis.) wasdissolved in 50 ml of acetone, and 0.532 ml of glycerol triglycidylether (Polysciences, Warrington, Pa.), and 3.3 g potassium carbonate(Aldrich Chemicals, Milwaukee, Wis.) were added to the solution. Thereaction mixture was heated to reflux over 24 hours. After 24 hours ofheating, thin layer chromatography (TLC) showed consumption of theglycerol starting material (eluent 20:1 Chloroform:methanol) and theemergence of three uv active spots. The acetone was removed by rotaryevaporation and the residue was dissolved in chloroform, and filtered.The resulting chloroform solution was washed three times with 4N NaOHaqueous solution, once with deionized water, then twice with 1N HClaqueous solution, and three times again with deionized water. Thechloroform solution was dried over magnesium sulfate, filtered, and thesolvent removed by rotary evaporation. The resulting oil was washedthree times with diethyl ether and dried. This treatment removed all4-hydroxybenzophenone starting material, with TLC revealing the samethree uv active spots. These three products presumably correspond tosingle, double, and triple substitution of benzophenone on the glycerolcompound.

Example 5 Diethylene Glycol Photocrosslinker Synthesis

4-Hydroxybenzophenone, 2.2758 g (11.4811 mMol, 2 mol eq, Alfa Aesar,Ward Hill, Mass.), was added to a 100 mL round bottom flask equippedwith a reflux condenser and dissolved in 75 mL of acetone. Ethyleneglycol diglycidyl ether, 1.0000 g (5.7405 mMol, 1 mol eq AldrichChemicals, Milwaukee, Wis.) followed by potassium carbonate, 3.1736 g(22.9621 mMol, 4 mol eq), was then added to the mixture and was heatedat reflux overnight. After cooling, the remaining solid was filtered andorganic layer was removed in vacuo. The crude product mixture wasredissolved in 60 mL of chloroform and the residual4-Hydroxybenzophenone was removed by washing with a 4N NaOH aqueoussolution. The organic layer was then dried over MgSO₄ and filtered toremove drying agent. A portion of the chloroform solvent was removed invacuo until 5 mL remained. The product was isolated by silica column(EMD Silica Gel 0.040-0.063 mm, 230-400 mesh, 60 Å) using (9:1) EthylAcetate:Hexane as eluent. Elution was monitored by TLC. R_(f) value ofdesired product was 0.40 in same eluent. ¹H NMR (CDCl₃): δ=7.7-7.9,7.4-7.6, 6.9-7.1 (m, characteristic of benzophenone), 4.2-4.3 (m),4.0-4.2 (m), 3.6-3.8 ppm (m).

Example 6 Synthesis of Urea Photo-Crosslinker

Bis-2,3-dihydroxypropylurea, 0.3000 g (1.4408 mMol, 1 mol equiv. AldrichChemicals, Milwaukee, Wis.), was added to a 50 mL round bottom flaskunder argon sweep and dissolved in 20 mL of DMF (Fisher Scientific,Pittsburgh, Pa.). Sodium hydride (60% dispersion in mineral oil, AldrichChemicals, Milwaukee, Wis.), 0.2305 g (5.7633 mMol, 4 mol eq), was thenadded and stirred at room temperature for 20 minutes.4-(Bromomethyl)benzophenone, 1.5858 g (5.7633 mMol, 4 mol equiv. AldrichChemicals, Milwaukee, Wis.), was added to the mixture and heated atreflux under positive argon pressure for five hours. After cooling, thereaction mixture was dissolved in 200 mL of deionized water and thecrude product was extracted with chloroform. The organic layer was thendried over magnesium sulfate and filtered to remove the drying agent.The chloroform was removed in vacuo and the crude product wasredissolved in a minimal amount of (85:15) CHCl₃:MeOH. The product wasisolated by silica gel column (EMD Silica Gel 0.040-0.063 mm, 230-400mesh, 60 Å) using (85:15) CHCl₃:MeOH as eluent. Elution was monitored byTLC. R_(f) value of desired product was 0.74 in the same eluent. Severalspots were isolated together and may represent two, three, and fourfunctionalized crosslinkers. ¹H NMR (CDCl₃): δ=7.3-7.9 (m,characteristic benzophenone pattern), 4.5-4.7 (m), 3.5-3.8 ppm (m).

Example 7 Synthesis of Polyalcohol Photo-Crosslinker

3,4-O-Isopropylidene-D-mannitol, 0.5000 g (2.2498 mMol, 1 mol eq,Aldrich Chemicals, Milwaukee, Wis.), was added to a 50 mL round bottomflask equipped with a reflux condenser and dissolved in 25 mL ofchloroform under argon sweep. NaH (with 60% dispersion in mineral oil,Aldrich Chemicals, Milwaukee, Wis.), 0.2700 g (6.7495 mMol, 3 mol eq),was added and then stirred for 30 minutes. 4-(Bromomethyl)benzophenone(Aldrich Chemicals, Milwaukee, Wis.), 0.1.23808 g (4.4996 mMol, 2 moleq), was added to the mixture and heated at reflux overnight underpositive argon pressure. After cooling, the organic layer was filteredto remove precipitate. A portion of the chloroform solvent was removedin vacuo until 5 mL remained. The product was isolated by silica gelcolumn (EMD Silica Gel 0.040-0.063 mm, 230-400 mesh, 60 Å) usingchloroform as eluent. Elution was monitored by TLC. R_(f) value ofdesired product was 0.40 in the same eluent. Three compounds wereisolated and may represent different isomers of the compound. ¹H NMR(CDCl₃): δ=7.3-7.9 (m, characteristic of benzophenone pattern), 4.6-5.0(dd), 4.5-4.6 (s), 3.6-3.9 (m), 1.5-1.6 ppm (s).

Example 8 Synthesis of Photo-Uracil Crosslinker

6-Aminouracil, 0.1091 g (0.8581 mMol, 1 mol eq, Aldrich Chemicals,Milwaukee, Wis.), was added to a 100 mL round bottom flask equipped witha reflux condenser and dissolved in 50 mL of chloroform under argonsweep. 4-(Benzoyl)benzoic acid chloride, 0.4199 g (1.7161 mMol, 2 moleq, Aldrich Chemicals, Milwaukee, Wis.), 4-Dimethylaminopyridine,0.01260 g (3-5 wt % of 4-(Benzoyl)benzoic acid chloride, AldrichChemicals, Milwaukee, Wis.), and Triethylamine, 0.1042 g (1.02969 mMol,1.2 mol eq, Aldrich Chemicals, Milwaukee, Wis.) were heated at refluxunder positive argon pressure overnight. After cooling, the reactionmixture was filtered to remove precipitate. The organic layer wasremoved in vacuo and the remaining crude reaction mixture wasredissolved in a minimal amount of (9:1) CHCl₃:MeOH. The desired productwas isolated by silica gel column (EMD Silica Gel 0.040-0.063 mm,230-400 mesh, 60 Å) using the (9:1) CHCl₃:MeOH as eluent. Monitorelution by TLC. R_(f) value of desired product was 0.56 in the sameeluent.

Example 9 Synthesis of TOB Crosslinker

6 g of triglycidyl isocyanurate (Aldrich Chemicals, Milwaukee, Wis.) and19.6 g of 2-hydroxy-4-(octyloxy)-benzophenone (Aldrich Chemicals,Milwaukee, Wis.) were mixed in a 50-ml round bottom flask containing amagnetic stir bar. The flask was flushed with argon for 10 min andheated to 130° C. in an oil bath. Once the reaction mixture melted, 26mg of triphenylphosphine (Aldrich Chemicals, Milwaukee, Wis.) was added.The mixture was stirred under argon for three days and cooled to roomtemperature. The product was purified by column chromatography (silicagel, 230-400 mesh, Whatman, Inc.) using 18:17 ethyl acetate/hexane aseluent (R_(f)˜0.66). The fractions containing the pure product werecombined and concentrated under reduced pressure and a yellowish syrupwas obtained after drying under vacuum (yield 68%).

The crosslinker is soluble in most common solvents including chloroform,methylene chloride, acetone, ethyl acetate, isopropanol, etc. ¹H NMR(CDCl₃) confirmed the structure of the product. The peaks at 7.72 ppm,7.40 ppm, 6.52 ppm (m, 24H) were the typical signals from benzophenone.The peak at d 4.05 ppm (m, 15H) was assigned to the protons of methyleneand methine groups at the ring opening site of epoxide. The peaks0.9-1.8 ppm (m, 45H) belonged to octyl group.

Example 10 Synthesis of BOB Crosslinker

Triphenylolmethane triglycidyl ether, 1.62 g (3.5 mMol), was added to adry 50 mL round bottom flask, followed by the addition of2-hydroxy-4-(octyloxy)-benzophenone, 2.88 g (8.8 mMol).Triphenylphosphine, 0.14 g (0.55 mMol), was then added and the mixturewas heated at 125° C. under positive argon pressure overnight. Aftercooling to room temperature, the product was purified by silica gelcolumn (EMD Silica Gel, 0.040-0.063 mm, 230-400 mesh, 60 Å) to give apale, yellow translucent syrup. Hexane:ethyl acetate (27:20) was used aseluent. R_(f) of desired product was 0.47 in the same eluent.

The product is soluble in most common organic solvents such as THF, IPA,CH₂Cl₂, CHCl₃, acetone and ethyl acetate and is partially soluble inhexane. ¹H NMR (CDCl₃): The peaks at 7.75 ppm, 7.45 ppm, 6.55 ppm (m,24H) were the typical signals from benzophenone. The peaks at 6.6-7.0ppm (m, 12H) were assigned to the protons of benzene. The peaks at3.5-4.1 ppm (m, 15H) corresponded to the protons of methylene andmethine groups at the ring opening site of epoxide. The peaks 1.2-1.9ppm (m, 45H) belonged to octyl group.

Example 11 Synthesis of TEG Crosslinker

1.94 g of tetraethylene glycol (Aldrich Chemicals, Milwaukee, Wis.) wasdried under vacuum at 50° C. for 2 h and dissolved in 50 ml anhydroustetrahydrofuran. 6.8 g of 4-(bromomethyl)benzophenone (AldrichChemicals, Milwaukee, Wis.) and 1.8 g sodium hydride (60% in mineraloil, Aldrich Chemicals, Milwaukee, Wis.) were added to the solution. Themixture was stirred overnight under reflux and argon protection. Thereaction solution was cooled to room temperature and filtered. Thefiltrate was concentrated by rotary evaporation and the residue waspurified by column chromatography (silica gel, 230-400 mesh, Whatman,Inc.) using 25:1 chloroform/methanol mixture as eluent. The fractionscontaining the pure product were combined and concentrated to dryness byrotary evaporation to yield yellowish oil (yield 80%).

The TEG crosslinker is soluble in most common solvents includingchloroform, methylene chloride, tetrahydrofuran, acetone, ethyl acetate,isopropanol, etc. ¹H NMR (CDCl₃) confirmed the structure of the product.The peaks at 7.49˜7.79 ppm (m, 18H) were the typical signals from4-subsituted benzophenone. The peak at 4.66 ppm (s, 4H) was assigned tothe protons of methylene connected to benzophenone groups. The peak at3.70 ppm (m, 16H) corresponded to ethylene groups.

Example 12 Synthesis of HEG Crosslinker

1.70 g of hexaethylene glycol (Aldrich Chemicals, Milwaukee, Wis.) wasdried under vacuum at 50° C. for 2 h and dissolved in 50 ml anhydroustetrahydrofuran. 3.7 g of 4-(bromomethyl)benzophenone (AldrichChemicals, Milwaukee, Wis.) and 1.5 g sodium hydride (60% in mineraloil, Aldrich Chemicals, Milwaukee, Wis.) were added to the solution. Themixture was stirred overnight under reflux and argon protection. Thereaction solution was cooled to room temperature and filtered. Thefiltrate was concentrated by rotary evaporation and the residue waspurified by column chromatography (silica gel, 230-400 mesh, Whatman,Inc.) using 25:1 chloroform/methanol mixture as eluent. The fractionscontaining the pure product were combined and concentrated to dryness byrotary evaporation to provide yellowish oil (yield 70%).

The HEG crosslinker is very soluble in most common solvents includingchloroform, methylene chloride, tetrahydrofuran, acetone, ethyl acetate,isopropanol, etc and slightly soluble in water. ¹H NMR (CDCl₃) confirmedthe structure of the product. The peaks at 7.26˜7.79 ppm (m, 18H) werethe typical signals from 4-subsituted benzophenone. The peak at 4.64 ppm(s, 4H) was assigned to the protons of methylene connected tobenzophenone groups. The peak at 3.66 ppm (m, 24H) corresponded toethylene groups.

Example 13 Coating with Different Binder Polymers and Crosslinkers

Super Hydrophobic Coating with TOB Crosslinker

400 mg of polyisobutylene (BASF Corp. Florham Park, N.J., Mw=2,000,000)and 23 mg TOB crosslinker were dissolved in 60 ml THF. 480 mg ofCAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.) weredispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee, Wis.,Mw=80,000) and 35 mg TOB crosslinker were dissolved in 30 ml THF. 720 mgof CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.)were dispersed in the solution with intensive vortexing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

Super Hydrophobic Coating with TEG Crosslinker

400 mg of polyisobutylene (BASF Corp. Florham Park, NJ, Mw=2,000,000)and 16 mg TEG crosslinker were dissolved in 60 ml THF. 480 mg ofCAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.) weredispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee, Wis.,Mw=80,000) and 24 mg TEG crosslinker were dissolved in 30 ml THF. 480 mgof CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.)were dispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

Super Hydrophobic Coating with HEG Crosslinker

400 mg of polyisobutylene (BASF Corp. Florham Park, N.J., Mw=2,000,000)and 18 mg HEG crosslinker were dissolved in 60 ml THF. 480 mg ofCAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.) weredispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee, Wis.,Mw=80,000) and 27 mg HEG crosslinker were dissolved in 30 ml THF. 480 mgof CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.)were dispersed in the solution with intensive vortexing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

Super Hydrophobic Coating with BOB Crosslinker

400 mg of polyisobutylene (BASF Corp. Florham Park, N.J., Mw=2,000,000)and 26 mg BOB crosslinker were dissolved in 60 ml THF. 480 mg ofCAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.) weredispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee, Wis.,Mw=80,000) and 39 mg BOB crosslinker were dissolved in 30 ml THF. 480 mgof CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.)were dispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

Super Hydrophobic Coating with ABC Crosslinker

400 mg of polyisobutylene (BASF Corp. Florham Park, N.J., Mw=2,000,000)and 10 mg 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (ABC,Aldrich Chemicals, Milwaukee, Wis.) were dissolved in 60 ml THF. 480 mgof CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.)were dispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee, Wis.Mw=80,000) and 15 mg 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone(ABC, Aldrich Chemicals, Milwaukee, Wis.) were dissolved in 30 ml THF.480 mg of CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola,Ill.) were dispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

Super Hydrophobic Coating with MBT

400 mg of polyisobutylene (BASF Corp. Florham Park, N.J., Mw=2,000,000)and 10 mg 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine(MBT, Aldrich Chemicals, Milwaukee, Wis.) were dissolved in 60 ml THF.480 mg of CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola,Ill.) were dispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Coming, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee, Wis.,Mw=80,000) and 18 mg2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine (MBT,Aldrich Chemicals, Milwaukee, Wis.) were dissolved in 30 ml THF. 480 mgof CAB-O-SIL® TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.)were dispersed in the solution with intensive vortex mixing.N-octyltrimethoxysilane (Dow Corning, Midland, Mich.) treated glassslides were dip coated by immersing the slides in the coating solutionfor 30 seconds, then extracting at 0.5 cm/sec. The slides were air driedat room temperature for 5 minutes, then irradiated with ultravioletlight (300 to 400 nm) for 5 minutes (Harland Medical UVM400, EdenPrairie, Minn.).

Super Hydrophobicity of Coated Slides

All formulations were able to create surfaces with water contact anglegreater than 150°, indicating the coatings were all super hydrophobic.

Solvent Challenging Test

The coated slides were sonicated on a probe sonicator for 1 min in THF.The slides were taken out and air dried. Water contact angles weremeasured on each coated surface. The results showed that all thecrosslinked surfaces remained super hydrophobic after THF challenging,while the non-crosslinked (same composition without crosslinker)coatings were washed away.

Example 14 Coating with Microparticles

200 mg of polyisobutylene (BASF Corp. Florham Park, N.J., Mw=2,000,000)was dissolved in 30 ml hexane. Coating solutions with three differentpolymer/particle ratios were made by dispersing 100 mg, 200 mg and 400mg of polystyrene beads (105˜125 micro, Polysciences, Inc, Warrington,Pa.) in the 30 ml polyisobutylene/hexane solution with intensive vortexmixing. N-octyltrimethoxysilane (Dow Corning, Midland, Mich.) treatedglass slides were dip coated by immersing the slides in the coatingsolution for 30 seconds, then extracting at 0.5 cm/sec. The slides wereair dried at room temperature for 5 minutes and water contact angleswere measured. The results showed that none of the microparticle coatingformulations could create a super hydrophobic or ultra hydrophobicsurface.

Example 15 Ultra Hydrophobic Coating of Fiber Membrane

A coating formulation containing 2.2 mg/ml polyisobutylene (BASF Corp.Florham Park, N.J., Mw=2,000,000), 2.6 mg/ml CAB-O-SIL® TS-720 silicananoparticles (Cabot Corp. Tuscola, Ill.) and 0.1 mg/ml triazinecrosslinker was made in tetrahydrofuran. 2×2 inch Reemay 2011 fibermembrane (BBA Fiberweb, Green Bay, Wis.) was coated by dipping themembrane in coating solution three times with 1 min interval. Themembranes were air dried at room temperature for 5 min and irradiatedunder UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt, 254 nm, 10 cmfrom light source) for 20 min. Coatings without crosslinker were made ascontrol.

Example 16 Ultra Hydrophobicity of the Coated Fiber Membrane

Both formulations (with and without triazine crosslinker) were able tocreate surfaces with water contact angle greater than 140° on fibermembrane, indicating the coatings were all ultra hydrophobic.

Example 17 Solvent Challenging Test of Coated Fiber Membrane

Solvent resistance of coatings with and without crosslinker was testedas follows. Coated samples were sonicated on a probe sonicator for 30seconds in methylene chloride. After rinsing with fresh methylenechloride the samples were air dried. Water contact angles were measuredon the treated samples. The results showed that the crosslinked coatingsremained ultra hydrophobic while the non-crosslinked coatings lost ultrahydrophobicity after solvent challenging.

Example 18 Separation of Aqueous/Organic Mixture Using Ultra HydrophobicFiber Membrane

Reemay 2011 fiber membrane was coated and crosslinked as describedabove. The membrane was installed on the bottom of a stainless steelcylinder with an O-ring seal. 10 ml water and 10 ml methylene chloridewere mixed and added on top of the coated membrane. Methylene chloridepassed though the membrane successfully and completely with 10 ml waterleft on top of the membrane. The uncoated membrane allowed bothmethylene chloride and water to pass through.

Although the present invention has been described with reference topreferred embodiments, persons skilled in the art will recognize thatchanges may be made in form and detail without departing from the spiritand scope of the invention. All references cited throughout thespecification, including those in the background, are incorporatedherein in their entirety. Those skilled in the art will recognize, or beable to ascertain, using no more than routine experimentation, manyequivalents to specific embodiments of the invention describedspecifically herein. Such equivalents are intended to be encompassed inthe scope of the following claim.

1. A composition comprising a cross linking compound of formula:L-((D-T-C(R¹)(XP)CHR²GR³C(═O)R⁴))_(m) wherein L is a linking groupcomprising a formula according to structure (I):

A, B and J form a ring, wherein A and J are C═O; B is NR¹¹; R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond; D isCR⁶R⁷; T is (—CH₂—)_(x), (—CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂—O—)_(x), or(—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond; R¹ is a hydrogen atom, an alkyl,alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group; X is O, S, orNR⁸R⁹; P is a hydrogen atom or a protecting group, with the provisiothat P is absent when X is NR⁸R⁹; R² is a hydrogen atom, an alkyl,alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group; G is an ester,ether, carbamate, thiocarbamate, sulfone, amide, urea, thiourea, amine,sulfonamide, imine, carbonyl, or (CH₂)_(t)—O—; R³ and R⁴ are eachindependently an alkyl, aryl, arylalkyl, heteroaryl, or anheteroarylalkyl group or when R³ and R⁴ are tethered together via(—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s) or (—CH₂—)_(r)S(O)₂(—CH₂—)_(s),(—CH₂—)_(r)NR(—CH₂—)_(s); R¹⁰ is a hydrogen atom or an alkyl, aryl orarylalkyl group; R⁶ and R⁷ are each independently a hydrogen atom, analkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl group; R⁸ and R⁹are each independently a hydrogen atom, an alkyl, aryl, or arylalkylgroup; R is a hydrogen atom, an alkyl or an aryl group; q is an integerfrom 1 to about 7; r is an integer from 0 to about 3; s is an integerfrom 0 to about 3; m is an integer from 2 to about 10; t is an integerfrom 1 to about 10; and x is an integer from 1 to about 500; a polymer;a particle having a particle size of between about 1 nm to about 25microns.
 2. (canceled)
 3. A composition comprising a cross linkingcompound of formula:L-(T-C(R¹)(XP)CHR²GR³C(═O)R⁴)_(m) wherein L is a linking groupcomprising a formula according to structure (I):

A, B and J form a ring, wherein A and J are C═O; B is NR¹¹; R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond with T; Tis (—CH₂—)_(x), (—CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂—O—)_(x) or(—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond; R¹ is a hydrogen atom, an alkyl,alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group; X is O, S, orNR⁸R⁹; P is a hydrogen atom or a protecting group, with the provisiothat P is absent when X is NR⁸R⁹; R² is a hydrogen atom, an alkyl,alkyloxyalkyl, aryl, aryloxylalkyl or aryloxyaryl group; G is an ester,ether, carbamate, thiocarbamate, sulfone, amide, urea, thiourea, amine,sulfonamide, imine, carbonyl, or (CH₂)_(t)—O—; R³ and R⁴ are eachindependently an alkyl, aryl, arylalkyl, heteroaryl, or anheteroarylalkyl group or when R³ and R⁴ are tethered together via(—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s) or (—CH₂—)_(r)S(O)₂(—CH₂—)_(s),(—CH₂—)_(r)NR(—CH₂—)_(s); R¹⁰ is a hydrogen atom or an alkyl, aryl orarylalkyl group; R⁸ and R⁹ are each independently a hydrogen atom, analkyl, aryl, or arylalkyl group; R is a hydrogen atom, an alkyl or arylgroup; q is an integer from 1 to about 7; r is an integer from 0 toabout 3; s is an integer from 0 to about 3; m is an integer from 2 toabout 10; t is an integer from 1 to about 10; and x is an integer from 1to about 500; a polymer; and a particle having a particle size betweenabout 1 nm to about 25 microns.
 4. A composition comprising a crosslinking compound of formula:L-(GTZR³C(═O)R⁴)_(m) wherein L is a linking group comprising a formulaaccording to structure (I):

A, B and J form a ring, wherein A and J are C═O; B is NR¹¹; R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond; T is(—CH₂—)_(x), (—CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond; G is an ester, carbamate,thiocarbamate, amide, urea, thiourea, imine, carbonyl, or (CH₂)_(t)—O—;Z is C═O, COO, or CONH when T is (—CH₂—)_(x); R³ and R⁴ are eachindependently an alkyl, aryl, arylalkyl, heteroaryl, or anheteroarylalkyl group or when R³ and R⁴ are tethered together via(—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s) or (—CH₂—)_(r)S(O)₂(—CH₂—)_(s),(—CH₂—)_(r)NR(—CH₂—)_(s); R is a hydrogen atom or an alkyl or arylgroup; q is an integer from 1 to about 7; r is an integer from 0 toabout 3; s is an integer from 0 to about 3; m is an integer from 2 toabout 10; t is an integer from 1 to about 10; and x is an integer from 1to about 500; a polymer; and a particle having a particle size ofbetween about 1 nm to about 25 microns.
 5. A composition comprising across linking compound of formula:L-(TGQR³C(═O)R⁴)_(m) wherein L is a linking group comprising a formulaaccording to structure (I):

A, B and J form a ring, wherein A and J are C═O; B is NR¹¹; R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond with T; Tis (—CH₂—)_(x), (—CH₂CH₂—O—)_(x), (—CH₂CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂CH₂—O—)_(x) or forms a bond; G is an ester, ether, carbamate,thiocarbamate, sulfone, amide, urea, thiourea, amine, sulfonamide,imine, carbonyl, or (CH₂)_(t)—O—; Q is (—CH₂—)_(p), (—CH₂CH₂—O—)_(p),(—CH₂CH₂CH₂—O—)_(p) or (—CH₂CH₂CH₂CH₂—O—)_(p); R³ and R⁴ are eachindependently an alkyl, aryl, arylalkyl, heteroaryl, or anheteroarylalkyl group or when R³ and R⁴ are tethered together via(—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s) or (—CH₂—)_(r)S(O)₂(—CH₂—)_(s),(—CH₂—)_(r)NR(—CH₂—)_(s); R¹⁰ is a hydrogen atom or an alkyl, aryl, oran arylalkyl group; R is a hydrogen atom or an alkyl or aryl group; q isan integer from 1 to about 7; r is an integer from 0 to about 3; s is aninteger from 0 to about 3; m is an integer from 2 to about 10; p is aninteger from 1 to about 10; t is an integer from 1 to about 10; and x isan integer from 1 to about 500; a polymer; and a particle having aparticle size of between about 1 nm to about 25 microns.
 6. Acomposition comprising a cross linking compound of formula:L-(-CH₂—)_(xx)C(R¹)(GR³C(═O)R⁴)_(m) wherein L is a linking groupcomprising a formula according to structure (I):

A, B and J form a ring, wherein A and J are C═O; B is NR¹¹; R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond; R¹ is ahydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalky, oraryloxyaryl group; each G is an ester, ether, carbamate, thiocarbamate,sulfone, amide, urea, thiourea, amine, sulfonamide, imine, carbonyl, or(CH₂)_(t)—O—; each R³ and R⁴ are each independently an alkyl, aryl,arylalkyl, heteroaryl, or an heteroarylalkyl group or when R³ and R⁴ aretethered together via (—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s),(—CH₂—)_(r)S(—CH₂—)_(s), (—CH₂—)_(r)S═O(—CH₂—)_(s) or(—CH₂—)_(r)S(O)₂(—CH₂—)_(s), (—CH₂—)_(r)NR(—CH₂—)_(s); each R¹⁰ is ahydrogen atom or an alkyl, aryl, or an arylalkyl group; each R is ahydrogen atom or an alkyl or aryl group; each q is an integer from 1 toabout 7; each r is an integer from 0 to about 3; each s is an integerfrom 0 to about 3; m is an integer from 2 to about 10; each t is aninteger from 1 to about 10; and xx is an integer from 1 to about 10; apolymer; and a particle having a particle size of between about 1 nm toabout 25 microns.
 7. A composition comprising a cross linking compoundof formula:L-(-C(R¹)(XP)CHR²GR³C(═O)R⁴)_(m) wherein L is a linking group comprisinga formula according to structure (I):

A, B and J form a ring, wherein A and J are C═O; B is NR¹¹; R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond; R¹ is ahydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl oraryloxyaryl group; X is O, S, or NR⁸R⁹; P is a hydrogen atom or aprotecting group, with the provisio that P is absent when X is NR⁸R⁹; R²is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl oraryloxyaryl group; G is an ester, ether, carbamate, thiocarbamate,sulfone, amide, urea, thiourea, amine, sulfonamide, imine, carbonyl, or(CH₂)_(t)—O—; R³ and R⁴ are each independently an alkyl, aryl,arylalkyl, heteroaryl, or an heteroarylalkyl group or when R³ and R⁴ aretethered together via (—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s),(—CH₂—)_(r)S(—CH₂—)_(s), (—CH₂—)_(r)S═O(—CH₂—)_(s) or(—CH₂—)_(r)S(O)₂(—CH₂—)_(s), (—CH₂—)_(r)NR(—CH₂—)_(s); R⁸ and R⁹ areeach independently a hydrogen atom, an alkyl, aryl, or arylalkyl group;R¹⁰ is a hydrogen atom or an alkyl, aryl, or an arylalkyl group; R is ahydrogen atom, an alkyl or an aryl group; q is an integer from 1 toabout 7; r is an integer from 0 to about 3; s is an integer from 0 toabout 3; m is an integer from 2 to about 10; and t is an integer from 1to about 10; a polymer; and a particle having a particle size of betweenabout 1 nm to about 25 microns.
 8. A composition comprising a crosslinking compound of formula:L-(GR³C(═O)R⁴)_(m); wherein L is a linking group comprising a formulaaccording to structure (I):

A, B and J form a ring, wherein A and J are C═O; B is NR¹¹; R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond; G is anester, carbamate, thiocarbamate, amide, urea, thiourea, imine, carbonyl,or (CH₂)_(t)—O—; R³ and R⁴ are each independently an alkyl, aryl,arylalkyl, heteroaryl, or an heteroarylalkyl group or when R³ and R⁴ aretethered together via (—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s),(—CH₂—)_(r)S(—CH₂—)_(s), (—CH₂—)_(r)S═O(—CH₂—)_(s) or(—CH₂—)_(r)S(O)₂(—CH₂—)_(s), (—CH₂—)_(r)NR(—CH₂—)_(s); R is a hydrogenatom, an alkyl or an aryl group; q is an integer from 1 to about 7; r isan integer from 0 to about 3; s is an integer from 0 to about 3; m is aninteger from 2 to about 10; and t is an integer from 1 to about 10; apolymer; and a particle having a particle size of between about 1 nm toabout 25 microns.
 9. A composition comprising a cross linking compoundof formula:L-(ZZ-D-T-C(R¹)(XP)CHR²GR³C(═O)R⁴)_(m) wherein L is a linking groupcomprising a formula according to structure (I):

A, B and J form a ring, wherein A and J are C═O; B is NR¹¹; R¹¹ is ahydrogen atom, an alkyl group, an aryl group or denotes a bond; ZZ is aphenyl group; D is CR⁶R⁷; T is (—CH₂—)_(x), (—CH₂CH₂—O—)_(x),(—CH₂CH₂CH₂—O—)_(x) or (—CH₂CH₂CH₂CH₂—O—)_(x); R¹ is a hydrogen atom, analkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group; X is O,S, or NR⁸R⁹; P is a hydrogen atom or a protecting group, with theprovisio that P is absent when X is NR⁸R⁹; R² is a hydrogen atom, analkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group; G is anester, ether, carbamate, thiocarbamate, sulfone, amide, urea, thiourea,amine, sulfonamide, imine, carbonyl, or (CH₂)_(t)—O—; R³ and R⁴ are eachindependently an alkyl, aryl, arylalkyl, heteroaryl, or anheteroarylalkyl group or when R³ and R⁴ are tethered together via(—CH₂—)_(q), (—CH₂—)_(r)C═O(—CH₂—)_(s), (—CH₂—)_(r)S(—CH₂—)_(s),(—CH₂—)_(r)S═O(—CH₂—)_(s) or (—CH₂—)_(r)S(O)₂(—CH₂—)_(s),(—CH₂—)_(r)NR(—CH₂—)_(s); R¹⁰ is a hydrogen atom or an alkyl, aryl orarylalkyl group; R⁶ and R⁷ are each independently a hydrogen atom, analkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl group; R⁸ and R⁹are each independently a hydrogen atom, an alkyl, aryl, or arylalkylgroup; R is a hydrogen atom, an alkyl or an aryl group; q is an integerfrom 1 to about 7; r is an integer from 0 to about 3; s is an integerfrom 0 to about 3; m is an integer from 2 to about 10; t is an integerfrom 1 to about 10; and x is an integer from 1 to about 500; a polymer;a particle having a particle size of between about 1 nm to about 25microns.
 10. A super hydrophobic composition comprising a photoreactivecross linking compound comprising a triazine, a polymer and a particlehaving a particle size of between about 1 nm to 25 microns.
 11. An ultrahydrophobic composition comprising a photoreactive cross linkingcompound comprising a triazine, a polymer and a particle having aparticle size of between about 1 nm to 25 microns.
 12. A compositioncomprising a crosslinking compound of formula:

a polymer; a particle having a particle size of between about 1 nm toabout 25 microns.